WO2013083293A1 - Système anti-corrosion pour l'acier - Google Patents

Système anti-corrosion pour l'acier Download PDF

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Publication number
WO2013083293A1
WO2013083293A1 PCT/EP2012/005102 EP2012005102W WO2013083293A1 WO 2013083293 A1 WO2013083293 A1 WO 2013083293A1 EP 2012005102 W EP2012005102 W EP 2012005102W WO 2013083293 A1 WO2013083293 A1 WO 2013083293A1
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Prior art keywords
steel substrate
sodium
coated steel
coating
manufacturing
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PCT/EP2012/005102
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English (en)
Inventor
Tapan Kumar Rout
Anil Vilas Gaikwad
Theo Dingemans
Mikhail Zheludkevich
Joao TEDIM
Kiryl YASAKAU
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Tata Steel Nederland Technology Bv
Tata Steel Limited
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Priority to EP12809115.4A priority Critical patent/EP2788437A1/fr
Publication of WO2013083293A1 publication Critical patent/WO2013083293A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers

Definitions

  • the present invention relates to a method of manufacturing a coated steel substrate, the coated steel substrate thus produced and to the use of the coated substrate in automotive, building or construction applications.
  • metal substrates such as steel corrode in oxidising environments and that such corrosion compromises the longevity of the substrate.
  • Metallic coatings may be applied to steel to inhibit corrosion, for instance by hot-dip galvanising, but the application of organic coatings in lieu of metallic coatings is deemed to offer a more cost effective approach.
  • Polymeric coatings primarily act as an impermeable physical barrier to prevent or at least reduce the underlying steel substrate from coming into contact with corrosive elements and/or compounds such as water, oxygen, corrosive chemicals or ionic salts such as NaCI.
  • corrosive elements and/or compounds such as water, oxygen, corrosive chemicals or ionic salts such as NaCI.
  • the corrosive entities can enter the damaged site to degrade the exposed steel substrate, and in certain instances accelerate the corrosion process.
  • polymeric coatings may be provided with corrosion inhibitors such as chromates, phosphates or zirconates which form a thin protective layer on the surface of the steel substrate, a so-called passivation layer, which prevents further corrosion by the corrosive entities.
  • corrosion inhibitors such as chromates, phosphates or zirconates which form a thin protective layer on the surface of the steel substrate, a so-called passivation layer, which prevents further corrosion by the corrosive entities.
  • passivation layer which prevents further corrosion by the corrosive entities.
  • a further disadvantage of providing polymeric coatings with corrosion inhibitors is that the corrosion inhibitors may react with the polymer precursor, i.e. before and/or during curing, which may cause the cured polymeric coating to exhibit reduced barrier properties.
  • organic coated strip products typically comprise a zinc or zinc alloy coated steel strip substrate having a passivation layer thereon, a polymeric coating as a primer and a topcoat.
  • Organic coated strip products comprising conventional primer layers are susceptible to blister formation and filiform corrosion which reduces the longevity of organic coated strip product.
  • Another challenge of such systems is to ensure that the polymeric coating is compatible with the conversion layer and the topcoat otherwise the topcoat and/or the primer will delaminate from the substrate surface.
  • One object of the invention is to provide a polymeric coating on a steel substrate, that when scratched, acts to inhibit the corrosion process.
  • Another object of the invention is to provide a polymeric coating that is more environmentally acceptable.
  • a further object of the invention is to improve the corrosion protective properties of polymeric coatings comprising corrosion inhibitors.
  • a further object of the invention is provide a polymeric primer coating that when used in organic coated strip products for building and construction applications reduces the formation of blisters and filiform corrosion.
  • a further object of the invention is to provide a polymeric primer coating that is compatible with both a zinc or zinc alloy coating and a topcoat.
  • the first aspect of the invention relates to a method of manufacturing a coated steel substrate for use in construction or automotive applications which comprises the steps of:
  • the method according to the first aspect of the invention has the advantage that corrosion inhibitors present in the coating do not adversely affect the stability and the barrier properties of the coating. Since the nanoscale corrosion inhibitors are contained in the nanocontainers prior to the step of combining the first and second coating mixtures, the possibility of the nanoscale corrosion inhibitors chemically interacting with the curable organic component and/or other components present in the coating mixture is avoided or at least reduced.
  • the inventors also found that when the coating of the coated steel substrate is damaged, for instance by abrasion, to an extent that a section of the steel substrate becomes exposed to the external environment, the nanoscale corrosion inhibitors are released from the nanocontainers in response to changes in pH, ionic strength and/or the presence of certain ions in a corrosive solution.
  • the 'intelligent' release of nanoscale corrosion inhibitors thus initiates a self-healing process that inhibits further corrosion of the substrate thereby increasing its working lifetime.
  • the nanocontainers comprise layered double hydroxides, halloysites, CaC0 3 , polymeric containers or mixtures thereof.
  • nanoscale corrosion inhibitors are released in response to a change in local surroundings (pH, ionic strength, corrosive solution), whereas in the case of polymeric containers, the nanoscale corrosion inhibitors are released when the polymeric container itself is damaged.
  • Preferred polymeric containers for instance in the form of a capsule, comprise polyurethane.
  • loaded LDH nanocontainers provide effective active corrosion protection during the early stages of corrosion, whereas loaded halloysites afford better long term active corrosion protection.
  • Polyetherimides which comprise a mixture of loaded LDH and halloysite nanocontainers are therefore characterised by improvements in both short and longer term active corrosion protection relative to polyetherimides comprising loaded LDH or halloysites alone.
  • Layered double hydroxides are a class of clay that have proven particularly effective as nanocontainers for the controlled release of nanoscale corrosion inhibitors.
  • Layered double hydroxides are layered clay materials comprising positively charged hydroxide layers that are separated by layers of anionic nanoscale corrosion inhibitors and water.
  • an exchange reaction occurs between the nanoscale corrosion inhibitor in the Layered double hydroxide and the corrosive anion, i.e. anionic nanoscale corrosion inhibitors are released into the solution and the corrosive anion is adsorbed into the layered double hydroxide structure thereby inhibiting the further corrosion of the steel substrate.
  • Halloysites are aluminosilicate clay minerals having a substantially hollow tubular structure, which makes them particularly suitable nanocontainers for receiving and entrapping nanoscale corrosion inhibitors.
  • Halloysites used in accordance with the invention have a length dimension between 20 nm and 25 ⁇ and have an internal diameter between 10 and 150 nm.
  • the halloysite has a particle size dimension between 1 and 15 ⁇ .
  • Nanocontainers may be defined as containers having nanoscale dimensions which are suitable for receiving and confining nanoscale corrosion inhibitors inside the nanocontainer. More specifically a nanocontainer may be defined by its internal diameter which should be in the nanometer range.
  • the nanocontainers have a particle size dimension between 20 nm and 25 ⁇ , preferably between 20 nm and 15 ⁇ , more preferably between 180 nm and 15 ⁇ .
  • the use of nanocontainers, e.g. between 20 nm and 25 ⁇ , but particularly between 20 and 180 nm means that active corrosion protection can be obtained over a large surface area at relatively low nanocontainer concentrations.
  • the steel substrate contains in weight %: 0 - 1.0% C, 0 - 5.0% Mn, 0 - 2.0% Si, 0 - 2.0 % Al and 0 - 1.0 % Cr.
  • Preferably small amounts of other alloying elements may also be present e.g. V, Nb, Ti and B.
  • the steel substrate is a carbon steel containing in weight %: 0.04 - 0.30 % C, 1.0 - 3.5 % Mn, 0 - 1.0 % Si, 0 - 1.0 % Al and 0 - 1.0 % Cr, preferably 0 - 0.2% C, 0 - 2.0% Mn, 0 - 0.6% Si, 0 - 1.0% Al and 0 - 0.6 % Cr, the remainder being iron and unavoidable impurities.
  • Other alloying elements such as Mo, P, Ti, V, Ni, Nb and Ta can be present but only in small amounts. Such carbon steels are preferred for building and construction applications.
  • the steel substrate is a TRIP steel, which contains in weight % 0.10 - 0.30 % C, 1.0 - 3.5 % Mn, 0.2 - 0.8 % Si and 0.5 - 2.0 % Al and 0 -1.0 Cr, preferably 0.10 - 0.20 % C, 1.0 - 2.0 % Mn, 0.2 - 0.6 % Si and 0.5 - 1.5 Al. It is preferred that Si + Al does not exceed 1.5 wt%.
  • the steel substrate is a TWIP steel that is suitable for use in automotive applications, which contains in weight % between 10 and 40 % manganese, preferably between 12 and 25 % manganese and up to 10 % aluminium. Both of the above TRIP and TWIP steels are preferred substrates for automotive applications.
  • the first coating mixture comprises 1-50 wt%, preferably 2.5-20 wt%, more preferably 2.5-10 wt% of nanocontainers with corrosion inhibitors contained therein.
  • a nanocontainer (with nanoscale corrosion inhibitors contained therein) content of 2.5-10 wt% was particularly effective at improving the barrier and active corrosion protection properties of the coating relative to coatings where nanocontainers (with nanoscale corrosion inhibitors contained therein) were absent from the first coating mixture. Further improvements in corrosion protection were possible, as the content of corrosion inhibitor loaded nanocontainers was increased up to 50 wt%.
  • coating mixtures comprising more than 50 wt % of nanocontainers were difficult to process and resulted in coatings having reduced barrier properties.
  • coating mixtures comprising less than 1 wt% of corrosion inhibitor loaded nanocontainers exhibited reduced active corrosion protection.
  • the nanocontainer is surface modified with a surface modifying component to provide a reactive functional group on the nanocontainer surface.
  • a surface modifying component to provide a reactive functional group on the nanocontainer surface.
  • the inventors found that by modifying the nanocontainer surface with a surface modifying component that the problems associated with nanocontainer agglomeration, particularly in water based solutions, were avoided or at least reduced to an extent that the nanocontainers could be uniformly distributed throughout the coating. Uniform distribution of the nanocontainers is preferred since thinner coating layers can be obtained. Moreover, uniform distribution ensures that active corrosion protection is not limited to localised areas of the coating but available throughout the whole of the coating layer.
  • Surface modifying the nanocontainers also has the advantage that the nanocontainer surface can be tailored to improve the interactions between the nanocontainer and the polymeric coating so as to avoid interface failure and improve barrier properties without having to provide an additional top-coat.
  • the surface modifying component comprises an organofunctional silane and a polyelectrolyte.
  • Organosilanes proved to be particularly effective as surface modifying components to improve the compatibility of the nanocontainers with the polymeric coating.
  • Another approach is to modify the nanocontainer surface with one or more layers of polyelectrolyte to form electrostatically connected layers on the nanocontainer, i.e. to form a polyelectrolyte shell. Using this approach the release properties of the nanocontainers may be tuned in such a way that the nanoscale corrosion inhibitors are only released in response to certain stimuli e.g. changes in pH.
  • the organosilane comprises alkylsilanes, arylsilanes, alkoxysilanes, aminosilanes or mixtures thereof.
  • the surface properties of the nanocontainers can be tailored by selecting organosilanes comprising different reactive functional groups.
  • Organosilanes comprising amine, carboxylic acid, isocyanate, ester and epoxy functional groups are particularly preferred.
  • the polyelectrolyte comprises polystyrenesulfonate (PSS), poly(allylamine hydrochloride (PAH), poly(anetholesulfonic acid sodium salt) (PAS), poly(4- vinylpyridine) (P4VP), polyethylenimine (PEI), poly(acrylic acid) (PAA).
  • PES polystyrenesulfonate
  • PAH poly(allylamine hydrochloride
  • PAS poly(anetholesulfonic acid sodium salt)
  • P4VP poly(4- vinylpyridine)
  • PEI polyethylenimine
  • PAA poly(acrylic acid)
  • PAA poly(acrylic acid)
  • the nanoscale corrosion inhibitors comprise anionic corrosion inhibitors and cationic corrosion inhibitors.
  • Preferred corrosion inhibitors all of which are suitable for loading in layered double hydroxides, halloysites and polymeric containers, include aluminium phosphate, sodium gluconate, sodium molybdate Na 2 Mo0 4 , cerium molybdate Ce2(Mo0 ) 3 , cerium nitrate Ce(N0 3 ) 3 , calcium nitrate Ca(N0 3 ) 2 , zinc sulfate ZnS0 4 , sodium tungstate NaW0 3 , sodium phosphomolybdate hydrate Na 3 Mo 12 0 4 oP, sodium phosphate Na 3 P0 4 , sodium hydrophosphate Na 2 HP0 4 , sodium dihydrophosphate NaH 2 P0 4 , sodium carbonate Na 2 C0 3 , sodium polyphosphate NaP0 3 x, sodium gluconate, 2- mercaptobenzothiazole, benzimidazole, quinal
  • the curable organic component comprises polyamic acid or a derivative thereof.
  • the curable organic component (polyamic acid) is converted into a polyetherimide polymer coating, which itself, affords the underlying steel substrate both corrosion and barrier protection.
  • This coating further acts as a matrix to support the uniformly dispersed nanocontainers to maintain the uniformity of the dispersion.
  • the polyamic acid comprises an aliphatic polyetherdiamine and preferably a polyetherdiamine that contains at least one primary amino group attached to the terminus of a polyether backbone, wherein the polyether backbone is based either on propylene oxide (PO), ethylene oxide (EO), or mixed EO/PO.
  • PO propylene oxide
  • EO ethylene oxide
  • mixed EO/PO mixed EO/PO
  • Particularly suitable first polyetherdiamines include 0,0'-Bis(2-aminopropyl) polypropylene glycol-Woc/ -polyethylene glycol-Woc -polypropylene glycol (J1 ), 4,7, 10- trioxa-1 ,13-tridecanediamine (J2), Polypropylene glycol) bis(2-aminopropyl ether having a molecular weight 230 (J3), Poly(propylene glycol) bis(2-aminopropyl ether having a molecular weight of 400 (J4) and 1 ,2- bis(2-aminoethoxyethane) (J5).
  • the glass transition temperature (Tg) of such polyamic acids is less than the Tg of polyamic acids comprising aromatic anhydrides and aromatic diamines and therefore lower temperatures may be employed to cure the combined coating mixture comprising the polyamic acid as organic curable component.
  • the content of the organic curable component in the second coating mixture is between 10 and 25 wt%.
  • the combined mixture is cured at a temperature between 80 and 250°C , preferably using Infrared, induction, electron beam or radiation heating.
  • the applied combined coating mixture is water based.
  • Such a coating mixture may be prepared in one of two ways.
  • a first approach comprises the step of preparing the first coating mixture and the second coating mixture in a water based solution and mixing the said solutions prior to applying the mixed solution on the substrate. This has the advantage that that the method does not make use of organic solvents, some of which are harmful, toxic and difficult to dispose of and handle.
  • a second approach comprises the steps of preparing the curable organic component in an organic solvent, precipitating the prepared organic curable component from the organic solvent, filtering and drying the precipitate and providing the dried precipitate in water to form a water based second coating mixture comprising the organic curable component.
  • the water based second coating mixture may then be mixed with a water based first coating mixture comprising the nanocontainers and nanoscale corrosion inhibitor contained therein to form a combined water based coating that is suitable for application on the steel substrate.
  • the advantage of preparing the organic curable component in organic solvent is that higher molecular weight organic curable components can be obtained, which once cured, result in coatings that exhibit increased formability and corrosion resistance relative to coatings comprising organic curable components that were prepared in water.
  • the steel substrate is provided with a corrosion protective coating prior to applying the combined mixture.
  • a corrosion protective coating comprises zinc or a zinc alloy wherein the zinc alloy comprises Zn as the main constituent, i.e. the alloy comprises more than 50% zinc, and one or more of Mg, Al, Si, Mn, Cu, Fe and Cr.
  • Zinc alloys selected from the group consisting of Zn- g, Zn-Mn, Zn-Fe, Zn- Al, Zn-Cu, Zn-Cr, Zn-Mg-AI and Zn-Mg-AI-Si are preferred and afford additional corrosion protection to the underlying steel substrate.
  • Corrosion protective coatings comprising silanes or zirconium improve the adhesion of the coating to steel substrate and are therefore also preferred.
  • the second aspect of the invention relates to the coated steel substrate produced according to the method of the first aspect of the invention.
  • the embodiments and the advantages relating to the first aspect of the invention similarly apply to the second aspect of the invention.
  • the dry film thickness of the coating is between 1 and 25 ⁇ , preferably between 3 and 10 ⁇ and more preferably between 3-6 ⁇ .
  • the nanocontainers of the present invention may have a length dimension up to 25 ⁇ , it is still possible to obtain a dry film thickness of the coating with the ranges specified above because the nanocontainers align parallel and not perpendicular to the substrate surface.
  • the third aspect of the invention relates to the use in an organic coated strip product for building and construction applications.
  • the coated steel substrate according to the second aspect of the invention may advantageously be used in an organic coated strip product for building and construction applications.
  • Organic coated steel products typically comprise a steel substrate, a zinc or zinc alloy coating, a passivation layer typically comprising chromium compounds, an organic primer and a top coat on the organic primer.
  • the polyetherimide coating of the invention exhibits very good corrosion protection, flexibility and adhesion properties to both the zinc or zinc alloy and the topcoat meaning that it is no longer necessary to provide an organic coated strip comprising a passivation layer. This has the advantage that the manufacture of organic coated strip products is made easier (less process steps), less expensive and more environmentally acceptable.
  • a further advantage is that the polyetherimide coating comprising corrosion inhibitor loaded nanocontainers reduce both the formation of blisters and filiform corrosion in the organic coated strip product. Moreover, in response to a change in local environment, the nanoscale container releases the nanoscale corrosion inhibitor contained therein for active corrosion protection.
  • the coated steel substrate according to the second aspect of the invention may also be used in the automotive industry where corrosion protection is of high importance.
  • the polyetherimide coating may replace zinc or zinc alloy corrosion protective coatings or supplement said zinc or zinc alloy coatings to further increase the level of corrosion protection afforded to the steel substrate.
  • Figure 1 shows a graph of polarisation resistance (R p ) as a function of immersion time for undoped polyetherimide coatings (A), polyetherimide coatings comprising 10 wt% sodium gluconate loaded halloysites (B), polyetherimide coatings comprising 10 wt% sodium gluconate loaded LDH that were aged in sodium chloride solution for 3 hours (C) and polyetherimide coatings comprising 10 wt% sodium gluconate loaded LDH that were aged in sodium chloride solution for 72 hours (D).
  • R p polarisation resistance
  • the loading of sodium gluconate corrosion inhibitors in LDH nanocontainers occurs via an ion- exchange reaction between an easily displaceable anion (e.g. chlorides, nitrates) and sodium gluconate.
  • an easily displaceable anion e.g. chlorides, nitrates
  • aqueous solution of sodium gluconate (0.1 M) (120 mL) was prepared and divided into a first portion (60 mL) and a second portion (60 mL).
  • LDH was added to the first portion under a nitrogen atmosphere to form a LDH dispersion and maintained under stirring for several hours (16-24h) at room temperature for the ion-exchange reaction to proceed.
  • the resulting slurry was centrifuged between 2000 and 25000 rpm and subsequently washed with distilled water. The procedure was repeated for the dispersion of LDH into the second portion of sodium gluconate solution.
  • the obtained LDHs were then dried in oven at 60°C for 8-16h and ball- milled to prevent the agglomeration of LDHs into micron-sized particles.
  • Example 3 Preparation of a water based polyamic acid solution
  • a 100 mL one necked vessel equipped with a nitrogen inlet is charged with 2,2' - (Ethylenedioxy)bis(ethylamine) J5 (3.5 mmol, 0.5187 g), m-phenylenediamine (1.5 mmol, 0.16 g) and NMP (23g).
  • 4,4-Biphthalic anhydride (5 mmol, 1.51 g) is added and this solution is stirred under inert conditions for 8 hrs to form polyamic acid.
  • N-butyldiethanol amine (5 mmol, 0.8g) is added to this stirred solution, which is stirred for an additional hour.
  • the stirred solution is then added to acetone or an acetone/methanol mixture under mechanical stirring causing the polyamic acid to precipitate.
  • the precipitate is dried at 50°C.
  • a 10 wt% solution of the dried precipitate is prepared in water; if necessary 1 wt % of N-butyldiethanol amine may be added to ease the dissolution.
  • Example 4 Preparation of a water based polyamic acid solution comprising nanocontainers and corrosion inhibitors
  • a dispersion of sodium gluconate loaded halloysite nanocontainers (30 wt%) was prepared in a water based solution according to the method of example 1. This solution was then added drop-wise to the water based polyamic acid solution under continuous mechanical stirring for a period of five minutes, after which the stirred solution was subjected to ultrasonic agitation for one minute to prevent halloysite agglomeration.
  • Active corrosion protection properties were determined using electrochemical impedance spectroscopy (EIS).
  • EIS electrochemical impedance spectroscopy
  • the experimental set up comprises a working electrode (coated steel substrate whose characteristics are to be evaluated), a reference electrode (calomel) and a counter electrode (Ni).
  • the working electrode area was selected using a Teflon holder that exposed a disk of area 12 cm 2 .
  • Impedance measurements were performed using an EG&G PARC 273A potentiostat and a Solartron 1255 frequency response analyzer controlled by a microcomputer running ZPLOT software (Scribner Associates, Charlottesille, VA). Impedance values were determined at five discrete frequencies per decade between 10 and 65 kHz.
  • the experimental data thus obtained was fitted with Randies' equivalent circuit model using ZSIM/CNLS software (Scribner Associates).
  • Polyetherimide coatings comprising sodium gluconate loaded halloysite or LDH nanocontainers were provided with two micro-defects to probe the active corrosion protective properties of the coatings.
  • the coated substrates were then immersed in a sodium chloride solution (0.05 M) and impedance spectra were obtained after 3, 30, 50, 75 and 100 hours of immersion (Fig 1).
  • the impedance measurements (R p ) show that enhanced corrosion protection is obtained when steel substrates are provided with a polyetherimide coating comprising sodium gluconate loaded halloysite or sodium gluconate loaded LDH nanocontainers relative to polyetherimide coated substrates in which the nanocontainers and corrosion inhibitors are absent.
  • the impedance measurements also show the effect of aging the nanocontainer/corrosion inhibitor mixture.
  • polyetherimide coatings comprising LDH and sodium gluconate that were aged in sodium chloride solution for 72 hours were characterised by an increase in polarisation resistance relative to those coatings which comprised LDH and sodium gluconate that were aged in sodium chloride only for 3 hours. Polarisation resistance is used to determine the rate of corrosion.
  • Polyetherimide coatings were doped with 2.5 wt%, 5 wt% or 10 wt% of sodium gluconate loaded halloysites or sodium gluconate loaded LDH (Table 1 and Table 2 respectively). Impedance measurements were obtained after 1 day and 14 days of immersion in sodium chloride solution (0.05 M).
  • sodium gluconate loaded halloysites afford better barrier properties relative to their LDH counterparts following the immersion of the coated substrates in saline solution for 14 days. This suggests that corrosion inhibitors are released from halloysites in a more controlled manner relative to corrosion inhibitors released from LDH. Thus, the advantageous effects of active corrosion protection are prolonged when halloysite nanocontainers are used.
  • the measurements also indicate that increasing the content of sodium gluconate loaded halloysites in the polyetherimide coating results in an improvement in the barrier properties of the coating. In contrast the best barrier properties were obtained when polyetherimide coatings comprise 2.5 wt% sodium gluconate loaded LDH.
  • Table 1 Assessment of barrier and active corrosion protection properties of doped polyetherimide coatings containing sodium gluconate loaded halloysites.
  • Table 2 Assessment of barrier and active corrosion protection properties of doped polyetherimide coatings containing sodium gluconate loaded LDH doped polyetherimide coatings.

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Abstract

L'invention concerne un procédé de fabrication d'un substrat en acier revêtu. Ce procédé comprend les étapes suivantes : (i) se procurer un substrat en acier ; (ii) préparer un premier mélange de revêtement comprenant des nanoconteneurs dans lesquels sont contenus des inhibiteurs de corrosion à l'échelle nanométrique ; (iii) préparer un second mélange de revêtement comprenant un composant organique durcissable ; (iv) combiner le premier mélange de revêtement et le second mélange de revêtement ; (v) appliquer le mélange combiné sur le substrat d'acier ; (vi) faire durcir le mélange combiné de façon à produire une structure en réseau dense du revêtement pour une protection contre la corrosion barrière et active du substrat d'acier.
PCT/EP2012/005102 2011-12-08 2012-12-10 Système anti-corrosion pour l'acier WO2013083293A1 (fr)

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ITTO20130416A1 (it) * 2013-05-23 2014-11-24 Fiat Ricerche Composizione di rivestimento per superfici metalliche con migliorate proprieta' anticorrosione
US9605162B2 (en) 2013-03-15 2017-03-28 Honda Motor Co., Ltd. Corrosion inhibiting compositions and methods of making and using
US9816189B2 (en) 2013-03-15 2017-11-14 Honda Motor Co., Ltd. Corrosion inhibiting compositions and coatings including the same
WO2018064721A1 (fr) 2016-10-04 2018-04-12 Commonwealth Scientific And Industrial Research Organisation Procédés anticorrosion
US20180244929A1 (en) * 2015-08-31 2018-08-30 Sumitomo Chemical Company, Limited Coating material for prevention of metal corrosion, and process for producing coating film for prevention of metal corrosion
US20190163061A1 (en) * 2017-11-24 2019-05-30 Taiflex Scientific Co., Ltd. Polyimide precursor and lithography pattern formed by the same
CN111607796A (zh) * 2019-02-25 2020-09-01 天津大学 一种可控释放的磁性锌铝铈水滑石负载2-巯基苯并噻唑缓蚀剂及其制备方法
WO2021014492A1 (fr) * 2019-07-19 2021-01-28 株式会社ジェーエフシーテック Charge anticorrosion utilisée dans une peinture organique, procédé de fabrication d'une charge anticorrosion et peinture
GB2593660A (en) * 2019-10-31 2021-10-06 Armadillo Metal Coatings Ltd Metallic coated substrates
CN113512337A (zh) * 2021-07-14 2021-10-19 苏州嘉乐威新材料股份有限公司 一种基于负载型腐蚀抑制剂改性的高粘接力环氧清漆及其制备方法
CN114206991A (zh) * 2019-06-28 2022-03-18 克林格贝格产品公司 聚合物阻燃剂及其制造方法
CN114277377A (zh) * 2021-03-03 2022-04-05 吕承洋 一种采用化学腐蚀处理铝/铝合金制基材表面并成膜使之能够被涂层附着的方法
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JP2016511300A (ja) * 2013-01-17 2016-04-14 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ 防食被膜の製造方法
WO2014111539A1 (fr) * 2013-01-17 2014-07-24 Basf Coatings Gmbh Procédé de production d'un revêtement anti-corrosion
US10392713B2 (en) 2013-03-15 2019-08-27 Honda Motor Co., Ltd. Corrosion inhibiting compositions and coatings including the same
US9605162B2 (en) 2013-03-15 2017-03-28 Honda Motor Co., Ltd. Corrosion inhibiting compositions and methods of making and using
US9816189B2 (en) 2013-03-15 2017-11-14 Honda Motor Co., Ltd. Corrosion inhibiting compositions and coatings including the same
US11136675B2 (en) 2013-03-15 2021-10-05 Honda Motor Co., Ltd. Corrosion inhibiting compositions and coatings including the same
US10988626B2 (en) 2013-03-15 2021-04-27 Honda Motor Co., Ltd. Corrosion inhibiting compositions and methods of making and using
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ITTO20130416A1 (it) * 2013-05-23 2014-11-24 Fiat Ricerche Composizione di rivestimento per superfici metalliche con migliorate proprieta' anticorrosione
US20180244929A1 (en) * 2015-08-31 2018-08-30 Sumitomo Chemical Company, Limited Coating material for prevention of metal corrosion, and process for producing coating film for prevention of metal corrosion
US10899935B2 (en) * 2015-08-31 2021-01-26 Sumitomo Chemical Company, Limited Coating material for prevention of metal corrosion, and process for producing coating film for prevention of metal corrosion
WO2018064721A1 (fr) 2016-10-04 2018-04-12 Commonwealth Scientific And Industrial Research Organisation Procédés anticorrosion
US11859104B2 (en) 2017-08-17 2024-01-02 Khalifa University of Science and Technology Mesoporous carbon based nanocontainer coatings for corrosion protection of metal structures
US20190163061A1 (en) * 2017-11-24 2019-05-30 Taiflex Scientific Co., Ltd. Polyimide precursor and lithography pattern formed by the same
CN111607796A (zh) * 2019-02-25 2020-09-01 天津大学 一种可控释放的磁性锌铝铈水滑石负载2-巯基苯并噻唑缓蚀剂及其制备方法
CN114206991A (zh) * 2019-06-28 2022-03-18 克林格贝格产品公司 聚合物阻燃剂及其制造方法
WO2021014492A1 (fr) * 2019-07-19 2021-01-28 株式会社ジェーエフシーテック Charge anticorrosion utilisée dans une peinture organique, procédé de fabrication d'une charge anticorrosion et peinture
GB2593660A (en) * 2019-10-31 2021-10-06 Armadillo Metal Coatings Ltd Metallic coated substrates
CN114277377A (zh) * 2021-03-03 2022-04-05 吕承洋 一种采用化学腐蚀处理铝/铝合金制基材表面并成膜使之能够被涂层附着的方法
CN114277377B (zh) * 2021-03-03 2024-03-26 吕承洋 一种采用化学腐蚀处理铝/铝合金制基材表面并成膜使之能够被涂层附着的方法
CN113512337A (zh) * 2021-07-14 2021-10-19 苏州嘉乐威新材料股份有限公司 一种基于负载型腐蚀抑制剂改性的高粘接力环氧清漆及其制备方法

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