EP3198054B1 - Oberflächenbehandlung von metallsubstraten - Google Patents

Oberflächenbehandlung von metallsubstraten Download PDF

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Publication number
EP3198054B1
EP3198054B1 EP15770520.3A EP15770520A EP3198054B1 EP 3198054 B1 EP3198054 B1 EP 3198054B1 EP 15770520 A EP15770520 A EP 15770520A EP 3198054 B1 EP3198054 B1 EP 3198054B1
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EP
European Patent Office
Prior art keywords
substrate
solution
layer
organophosphorus compound
stainless steel
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EP15770520.3A
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English (en)
French (fr)
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EP3198054A1 (de
EP3198054C0 (de
Inventor
Fabrice Lallemand
Xavier ROIZARD
Jean-Marie MELOT
Aurélien BUTERI
Mélanie BORGEOT
Romain EVRARD
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Universite de Franche-Comte
Aperam SA
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Universite de Franche-Comte
Aperam SA
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Publication of EP3198054C0 publication Critical patent/EP3198054C0/de
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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
    • C23C22/05—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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/07—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 aqueous acidic solutions with pH less than 6 containing phosphates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
    • 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
    • C23C22/02—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 non-aqueous solutions
    • C23C22/03—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 non-aqueous solutions containing phosphorus 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • 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
    • C23F11/1676—Phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/0603—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/245—Soft metals, e.g. aluminum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/246—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/247—Stainless steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/023—Multi-layer lubricant coatings

Definitions

  • the present invention relates to a process for the surface treatment of metal substrates, in particular stainless steel, with a view to improving their properties, in particular the tribological characteristics during their shaping, in particular by stamping.
  • stainless steel has now become the reference material in many fields such as automotive, consumer goods, heavy industry, microtechnology or electronics.
  • the preparation of the finished product requires at least one forming operation, for example stamping for flat products.
  • the range in which a metal is deformed without necking or breaking depends to a large extent on the performance of the lubricant used.
  • the patent US 4,048,374 relates to a process for treating metal surfaces allowing them to be protected against corrosion, in particular salt water.
  • This patent describes in particular the application of an organophosphonic acid ester solution on the metal substrate followed by the application of an organic substance such as paint, resin varnish, etc.
  • the patent application WO-A-99/66104 relates to a treatment to prevent the formation of stains (in particular water stains) on aluminum substrates.
  • This application describes in particular the application of a solution containing octadecylphosphonic acid on an aluminum substrate with a view to forming Al-OP bonds and, through this, a hydrophobic layer.
  • An object of the present invention is to provide a surface treatment solution capable of replacing existing industrial lubricants, which would not have the disadvantages mentioned above, in particular environmental.
  • Another object of the present invention is to provide metal substrates having tribological properties, in particular during their shaping.
  • Another object of the invention is to propose a method making it possible to confer on metal substrates the properties required to enable them to be shaped, in particular by stamping, without the use of a separate additional lubricant.
  • Yet another object of the present invention is to provide such a method making it possible to improve the tribological properties of a metal substrate during its shaping.
  • a treatment in which the surface of the metal substrate comprising surface hydroxyl groups is brought into contact with a solution of organophosphorus compounds so as to form a coating composed of a first chemisorbed layer on the metal surface in which the organophosphorus compounds are organized in the form of a monomolecular layer and of a second layer of physisorbed organophosphorus molecules at least predominantly crystallized.
  • the first monomolecular layer generally comprises bonds of the covalent type with hydroxyl groups present at the surface of the metal substrate.
  • Organophosphorus compounds can be considered therein as being chemisorbed.
  • the first layer thus exhibits strong adhesion to the substrate.
  • the constituent molecules of the second layer on the other hand, have weak bonds with the substrate, of the Van-der-Waals force type.
  • Organophosphorus compounds can be considered as physisorbed therein (see figure 1 ).
  • This second layer at least predominantly crystallized (that is to say crystallized for at least 50% of its mass and of its molecules), in fact exhibits less adhesion to the substrate.
  • the process of the invention confers very advantageous properties on metallic substrates, in particular as regards their tribological properties during their shaping.
  • organophosphorus compounds formed as described above has astonishing lubricating qualities, comparable or even superior to those of the best lubricants available on the market.
  • the coating deposited according to the invention confers an improved resistance of the metallic substrate to corrosion.
  • the metal substrates treated according to the invention can therefore be lubricated well before they are shaped, which has significant advantages.
  • the lubricating coating contributes to easy handling, reduces the risk of corrosion, especially during transport, and greatly facilitates subsequent shaping, since it makes it possible to dispense with the use of a separate additional lubricant. , usually in the form of an oil or polymer coating, while not degrading the lubrication performance and preserving the integrity of the tools vis-à-vis premature wear.
  • the process of the present invention therefore offers a high-performance solution for the treatment of metal substrates suitable for shaping processes, in particular stamping, both in economic terms and in environmental terms.
  • organophosphorus compounds used are not very toxic and can be implemented in a not very toxic solvent, in particular an alcohol and/or water, a 100% alcoholic solution (including ethanol, in particular absolute ethanol , is a preferred example) being preferred.
  • a 100% alcoholic solution including ethanol, in particular absolute ethanol , is a preferred example
  • the implementation of such a solution therefore does not give rise to regulatory difficulties, and its elimination does not pose any risks for the environment.
  • organophosphorus compounds are used in solution, which reduces the quantity required to confer the desired properties compared to oils, and further contributes to the economic and ecological interest of the process of the invention.
  • the organophosphorus compounds are used in the process of the invention in the form of a solution.
  • the solvent preferably comprises an alcohol, in particular a alkanol chosen from methanol, ethanol, propanol, isopropanol and butanol, and/or water.
  • the organophosphorus compound solution used has a concentration of more than 1 mM/l and preferably of 10 to 1000 mM/l, in particular from 20 to 500 and very particularly from 50 to 200 mM/l, advantageously from 20 to 500 mM/l and most particularly from 50 to 200 mM/l.
  • the organophosphorus compound solution is supersaturated.
  • the substrate treated by the method of the invention may in particular be a substrate made of iron, nickel, cobalt, aluminum, copper, chromium, titanium, zinc, gold, silver, ruthenium, rhodium or one of their alloys, in particular steels such as stainless steels, carbon steels and electrical steels.
  • It may in particular be a substrate made of iron, nickel, cobalt or one of their alloys.
  • it may be a substrate of aluminum, copper, chromium, titanium, zinc, gold, silver, ruthenium, rhodium or one of their alloys.
  • the metal substrate may in particular be a flat product.
  • the inventors discovered unexpectedly that a metallic substrate treated according to the invention exhibited tribological properties during its shaping that were superior or equivalent to a substrate treated with conventional lubricating oils. It has also been found, incidentally, that such a treatment was capable of giving the metal substrate a substantially improved resistance to corrosion.
  • the surface of the metallic substrate is first of all grafted with a very thin, monomolecular layer of organophosphorus compound.
  • the grafting takes place by reaction of the phosphonic groups with at least some of the hydroxyl groups present on the surface of the metal.
  • the first layer is linked to the substrate by bonds of the covalent type, and adheres firmly to the metallic surface.
  • the monomolecular layer can further be self-assembled. But this is not at all an obligation, which allows rapidity and simplicity of implementation of the processing in terms of time and number of steps.
  • An advantage of the process according to the invention in an industrial application, is precisely that it does not require giving the monomolecular layer time to self-assemble, and even does not require the monomolecular layer to coat the entire of the surface of the substrate. A coating of at least 15% of the surface of the substrate is already sufficient.
  • the shaping can be carried out almost immediately after the coating of the substrate, as soon as the solvent has evaporated. On the other hand, it becomes preferable to work with high concentrations of organophosphorus compound in the solvent, optimally in supersaturation.
  • self-assembled monolayer we mean a layer which can be defined as a molecular assembly which forms spontaneously over time by immersing a substrate in a solution containing an active surfactant, until a monolayer is formed. perfectly ordered.
  • the coating of the metal substrate further comprises, disposed on said monomolecular layer, a second layer of physisorbed molecules of organophosphorus compound at least predominantly crystallized.
  • a second layer of physisorbed molecules of organophosphorus compound at least predominantly crystallized.
  • at least predominantly it is meant that at least 50% of the compound is in crystallized form.
  • This second layer is significantly thicker compared to the first layer. Most often, it is possible to detect its presence with the naked eye.
  • the second layer occupies at least 15% of the reactive sites, the second layer is not everywhere linked to the substrate by strong bonds of the covalent type, all the more so since the second layer is at least mainly crystallized.
  • the adhesion of the second layer therefore results from other bonds, for example of the Van der Waals type, in particular with the underlying organophosphorus molecules grafted to the metal.
  • This second layer can be considered as physisorbed.
  • the molecules of organophosphorus compound are also at least predominantly crystallized.
  • Treated metal substrates have distinct characteristics from untreated substrates, particularly in terms of tribological properties during their shaping. These characteristics make it possible to envisage their shaping without the use of additional conventional lubricant, in particular without lubricant in the form of oil or of polymer.
  • Such substrates also advantageously have better resistance to corrosion, in particular during storage and transport.
  • the preferred organophosphonic compounds of formula (I) are those in which Z represents a functional group chosen from carboxylic acid, thiol or silane or in which Z is absent.
  • Organophosphorus compounds have moieties of different polarities.
  • the end comprising the phosphonic group is polar and has an affinity for the hydroxyl groups.
  • the phosphonic group reacts by an acid/base reaction with the surface oxide of the substrate and forms a strong semi-covalent bond between the molecule and the substrate. The organophosphonic end is therefore attached to the metal surface.
  • the organophosphorus compounds may comprise a less polar group, for example an optionally substituted carbon chain tending to give them a preferential orientation with respect to the metal surface.
  • This preferential orientation ultimately results in a perfectly ordered self-assembled monolayer.
  • the resulting order is also called self-assembly.
  • this characteristic is not obligatory, and the material may be shaped industrially before this state of self-assembly is reached.
  • the present invention also relates to a process for treating metallic substrates making it possible to improve their tribological behavior during their shaping, and even also their resistance to corrosion.
  • this process is characterized by the deposition on the substrate of a coating of organophosphorus compound, the particularity of which is that the compound is there in a double form.
  • the coating comprises a first monomolecular layer not necessarily self-assembled, which is in contact with at least 15% of the surface of the substrate, and is linked to the substrate by means of bonds of the covalent type, and, above this first layer (and above the substrate in the areas where it is not covered by the first layer, if there is one), it comprises a second layer in which the compound is both in physisorbed form and , at least predominantly crystallized, with low adhesion of the second layer to the first layer, and also to the substrate in any areas not covered by the first layer.
  • organophosphorus compound in these two distinct forms that allows the desired technical effects to be obtained, without the need to add other compounds to the treatment solution, or an additional layer of any product. on the surface of the material to be shaped.
  • the method of the invention can be used on substrates of various natures and shapes.
  • the metal must be oxidizable, spontaneously or not, and therefore likely to have hydroxyl groups on the surface.
  • they may be substrates based on iron, nickel, cobalt, aluminium, copper, chromium, titanium, zinc, gold, silver, ruthenium, rhodium or based on one of their alloys such as stainless steels , carbon steels or electrical steels.
  • the metal substrate may be a solid metal substrate or, optionally, a composite substrate, but it will have a surface which is at least partially metal.
  • the metallic substrate In order to dispose of the hydroxyl groups on the surface, it is generally not necessary to subject the metallic substrate to a particular treatment. Indeed, with the exception of certain metals or alloys, the ambient conditions are sufficient to oxidize the surface, thus creating the hydroxyl groups reactive with the phosphonic function.
  • the metal can be a pure metal but most often it will be a metal alloy.
  • steels in particular stainless steels, carbon steels, electrical steels (Fe-Si) but also high value-added ferrous alloys (Fe-Ni, Fe-Co).
  • Fe-Si electrical steels
  • Fe-Ni high value-added ferrous alloys
  • it can also be non-ferrous metals such as aluminium, copper, chromium, nickel, cobalt, titanium, zinc, gold, silver, ruthenium and rhodium or their alloys.
  • the shape of the substrate can be very variable.
  • a substrate for example, flat products intended, in particular, to be stamped, with a thickness of between 0.04 mm and 20 mm, with a preference for a thickness of between 0.4 and 2.5 mm, tubes, wires, or even products intended for cutting (in particular for substrates whose thickness is less than 4 mm).
  • step (ii) of the process makes it possible to bring the metal surface into contact with the organophosphorus compounds in solution.
  • This step can be carried out by various conventional means, for example by the Langmuir Blodgett technique, by immersion in a bath of solution, by spraying the solution, by application with a roller or even by spreading called spin coating.
  • the contacting is carried out by spraying the solution containing the organophosphorus compounds onto the metal substrate.
  • This method of bringing into contact is particularly advantageous because it is rapid and therefore compatible with an industrial rate. Unexpectedly, it was found that the quality of the coating formed is sufficient to significantly improve the tribological properties.
  • the time required for bringing into contact to obtain an optimal result from the tribological point of view can vary according to the reactivity of the substrate and that of the organophosphorus compounds chosen. It may also depend on other parameters such as temperature and concentration of the solution. However, the reaction is generally considered sufficient after contacting for a time which may be as little as one or a few seconds.
  • the duration of contacting the metal surface with the solution of organophosphorus compounds is preferably from 1 second to 600 minutes, better still from 1 to 60 seconds.
  • the process of the invention does not require any heavy or expensive equipment. It is fast and can be carried out on large surfaces.
  • the grafting of the surface of the metal substrate is carried out by contact with a solution of organophosphorus compound.
  • one of the advantages of the process is based on the effectiveness of the organophosphorus compounds. Given their good solubility in water and/or common alcohols, it appears advantageous to use the compound in the form of a solution.
  • the organophosphorus compounds of formula (I) are for the most part soluble in water and/or one of the alcohols chosen from methanol, ethanol, propanol, isopropanol and butanol.
  • Non-deaerated absolute ethanol is a preferred example, due to its low cost, low evaporation temperature and moderate toxicity.
  • the absence of dissolved oxygen in the solvent is not essential, as the duration of exposure of the organophosphorus compounds to the solvent may be low, and the dissolved oxygen then does not have time to denature them.
  • the concentration of the solution of organophosphorus compounds can in certain embodiments of the method have an impact on the quantity of physisorbed compound formed on the surface of the metal.
  • the method is not limited to a specific concentration range. It is only necessary to ensure that the quantity of organophosphorus compound deposited on the metal surface is sufficient to form both a chemisorbed monomolecular layer and a second physisorbed layer that is at least predominantly crystallized.
  • the treatment solution comprises more than 1, and preferably 10 to 1000, advantageously 20 to 500 and most particularly 20 to 50 mM/l of organophosphorus compound of formula (I) above.
  • a supersaturated solution of the organophosphorus compound(s) is used, knowing that in the range of 20 to 50 mM/l, for the preferred molecules envisaged, this supersaturation is already reached.
  • the solution may also contain other additives customary in the field, such as preservatives, emulsifiers, pigments or even additives for resistance to high pressures.
  • the solution of organophosphorus compounds can be prepared in a conventional manner.
  • the organophosphorus compounds are introduced into the solvent, although the reverse can also be done.
  • the solution can be stirred and, if necessary, heated.
  • the halogenated derivative zA-Br (200 mmol) is heated to 200° C. (oil bath) and the triethylphosphite (210 mmol) added drop by drop at this temperature for 30 minutes, while the bromoethane formed is distilled continuously ( steam temperature below 40°C). The mixture is then brought to 220-225° C. and maintained at this temperature for 20 minutes. Excess triethylphosphite is removed at 50-100 mm Hg for 5-10 min and the resulting oil cooled to room temperature. Concentrated aqueous hydrochloric acid (12 M, 250 ml) is added and the heterogeneous mixture brought to the boil with good stirring for 15 h.
  • Table 1 shows the compositions of the grafting solutions obtained in the various examples A1 to A10.
  • Table 1 Composition of the grafting solutions EXAMPLES Solution Group A Concentration (mol/l) A1 1 C16 straight alkyl 0.001 A2 1 C16 straight alkyl 0.005 A3 1 C16 straight alkyl 0.01 A4 1 C16 straight alkyl 0.05 AT 5 1 C16 straight alkyl 0.1 A6 2 C16 straight alkyl 0.001 A7 2 C16 straight alkyl 0.005 AT 8 2 C16 straight alkyl 0.01 A9 2 C16 straight alkyl 0.05 A10 2 C16 straight alkyl 0.1
  • a metal substrate consisting of an austenitic stainless steel sheet of grade 189 ED (1.4301-304) or ferritic stainless steel of grade 441 (1.4509-441) with a thickness of 1 mm respectively, was treated with the treatment solution prepared as indicated above according to the following procedure.
  • the substrate is initially degreased and cleaned by immersion in absolute ethanol and ultrasonic treatment for 5 minutes.
  • the substrate thus prepared is subsequently immersed in the chosen treatment solution for a time of 1 second, 30 minutes (0.5h), 2h and 16h, respectively.
  • the substrate is not rinsed after treatment. In fact, this would lead to the elimination of the layer of physisorbed organophosphorus compound, mainly crystallized, to retain only the monomolecular layer. The improvement of the tribological properties would then be insufficient, and the process would not be a viable solution compared to a treatment using oils.
  • the samples were specially rinsed at the end of the treatment in order to remove the physisorbed layer.
  • the surface tension was then evaluated before and after treatment of the substrate with the A5 solution (with rinsing) for the stainless steel substrates (ferritic and austenitic).
  • the surface tension which is different for each of the untreated substrates, tends to harmonize for the treated substrates, at a value close to 18.5 mJ/m 2 , testifying in fact to the sole contribution of the monomolecular layer in the apparent surface tension of the sample tested when the immersion time justifies the existence of a monomolecular layer sufficient to obtain this effect, said immersion time possibly being 2 h, or even less , according to the given experimental results.
  • the treated samples were characterized by means of a drawing/plane type tribometer, representative of the stamping conditions.
  • the rubbing parts are cylindrical and come into direct linear contact (or pseudo-linear if one considers a Hertz contact pressure) with the substrate to be tested by means of two arms forming a clamp, actuated by a pneumatic jack.
  • the cylinders are made of Z160CD12 tool steel. They exert a normal average force (perpendicular to the surface of the treated substrate) of 4000 N and are driven by a defined speed of 10 mm/min.
  • the coefficient of friction measured is of the order of 0.05 at the end of a treatment recommended by the present invention and proves to be constant during the various passes. This denotes very good tribological behavior, which moreover has no obvious alteration over time.
  • the results demonstrate a very marked improvement in the tribological properties by the treatment according to the method of the invention.
  • the metals treated according to the invention have a coefficient of friction lower than that obtained by treatment with a high-performance oil according to the state of the art.
  • the ability to draw is an important factor in the shaping of materials. Indeed, a metal having a good aptitude for stamping authorizes the use of severe industrial stamping conditions making it possible in particular to minimize the number of passes required to give the substrate the desired shape.
  • This aptitude for drawing is a complex combination of the elastoplastic mechanical properties of the material, the lubrication conditions and the process parameters used (type of tools, kinematics of the tools, etc.).
  • the treated substrates were characterized by drawing according to a necked type deformation path through the determination of the LDR ("Limit Drawing Ratio", or drawing limit ratio) for different lubrication conditions.
  • LDR Line Drawing Ratio
  • the diameter D of the stamped disc is increased by successive steps of 4 mm, until the first broken part is obtained.
  • This ratio is characteristic of each metal substrate and the associated lubrication conditions.
  • the comparison between a sheet lubricated with a common industrial oil and a sheet treated by the present invention therefore makes it possible to characterize the effectiveness of the lubricant proposed here, with properties strictly equivalent materials and process parameters.
  • Table 6 summarizes the results thus obtained for stainless steel substrates of the austenitic (1.4301 - 304) and ferritic (1.4509 - 441) types in various lubrication configurations. Note that the tools are made of uncoated Z160CDV12 steel, without any modification during the various tests. The data relating to ferritic (1.4509 - 441) and austenitic (1.4301 - 304) stainless steels are taken up respectively by the figure 6 And 7 .
  • a first series of tests was carried out on a grade of austenitic stainless steel 304 treated according to Example 19 or untreated according to the invention but coated with various conventional lubricants ( figure 7 ).
  • a second series was carried out on a grade of ferritic stainless steel 441 treated according to different examples, namely examples 61, 65, 69, 73, 59 and 59 with the addition of a voluntary post-treatment rinsing in order to to remove, for this last configuration, the second layer of molecules of organophosphorus compound at least predominantly crystallized.
  • tests were carried out on untreated sheet metal but coated with various conventional lubricants ( figure 6 ).
  • Renoform ETA lubricant is a chlorinated mineral oil commonly used industrially
  • solid lubricating paste Molykote G-Rapid Plus is a product used on a laboratory scale (or low series non-automated production) with a very high lubricity rarely equaled by conventional industrial oils.
  • the substrates obtained according to the invention exhibit, on stamping, characteristics that are equivalent to, or even superior to, those obtained by using high-performance lubricants.
  • a clear effect of the initial concentration of organophosphorus molecules on performance is highlighted by these results: a higher concentration induces much better product performance.
  • the test carried out according to Example 59 with removal of the second layer of molecules of organophosphorus compound (F) demonstrates the need to retain this second layer of molecules physisorbed at least predominantly crystallized to increase the performance of the product, and this, although the monomolecular layer obtained by the treatment of Example 59 induces a high degree of recovery.
  • the substrate obtained according to the invention exhibits, upon stamping, characteristics and performances clearly superior to those of equivalent substrates which are untreated but coated with more conventional lubricants dedicated to the production of large or small series. .
  • the performance gain inherent in a treatment according to the present invention is here estimated at 10%.
  • FIG 9 illustrates the results obtained on an austenitic stainless steel substrate (1.4301 - 304) treated according to example 33 (curve B) or untreated but coated with a MotulTech Cadrex DR136P industrial lubricant, which is a chlorinated lubricant commonly used on this tool of production (curve A). Said lubricant also requires a costly post-drawing degreasing step. Note that an important difference exists between the two series of parts produced illustrated by the figure 9 in this which concerns the initial lubrication conditions before stamping.
  • Table 8 Experimental conditions of the voltammetry test Three-electrode electrochemical cell working electrode Substrate to be tested Counter electrode Platinum Reference electrode Saturated Calomel Solvent HCl 0.5%, ventilated room temperature Scanning speed 10mV/s
  • the curves obtained correspond to voltammograms indicating the current density as a function of the potential applied to the metal immersed in the hydrochloric acid solution.
  • the behavior of the stainless steel sheets is greatly modified by the treatment according to the invention.
  • the treatment according to the invention reduces, at equivalent applied potential, the current density significantly. It is thus possible to define blocking rates of 99% and 95% respectively, corresponding to a marked corrosion-inhibiting effect of our invention.
  • the process of the invention allows access to metal substrates having advantageous characteristics such as a low coefficient of friction, an excellent ability to be drawn, and moreover, advantageously, a high resistance to corrosion.
  • the method is simple and quick to implement and does not require any specific equipment. It uses small quantities of low-toxic and low-cost compounds.
  • the economy of the use of a lubricating oil during transformation allows substantial savings, including on indirect costs (labour, degreasing equipment, etc.), and avoids the production of potentially dangerous waste for the environment.
  • the metal substrates treated by the method of the invention have substantial advantages since they greatly facilitate, due to their pre-lubrication, their subsequent shaping and are moreover protected against corrosion.
  • the surface treatment of metal substrates according to the invention by depositing a coating of organophosphorus compounds in different forms, therefore provides a real improvement in the tribological properties of the material without requiring a conventional lubricant in addition to said coating.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemically Coating (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Lubricants (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Claims (10)

  1. Metallsubstrat, dessen Oberfläche mit mindestens einer Organophosphorverbindung in Form einer ersten monomolekularen Schicht beschichtet ist, die mindestens 15 % der Oberfläche des Substrats beschichtet, und einer zweiten Schicht aus Organophosphormolekülen, von denen mindestens 50 % kristallisiert sind, wobei die zweite Schicht auf der ersten Schicht physisorbiert ist, wobei die Organophosphorverbindung die Formel (I) hat:
    Figure imgb0007
     wobei:
    A einen gerad- oder verzweigtkettigen, gesättigten oder ungesättigten Kohlenwasserstoff darstellt, der 14 bis 18 Kohlenstoffatome umfasst, wobei die Kette durch eine oder mehrere Gruppen substituiert werden kann, die ausgewählt werden aus Hydroxy, Amino, Cyano, Halogen, Sulfonsäure, Organophosphon und/oder unterbrochen durch ein oder mehrere Atome oder Gruppen, die ausgewählt werden aus O, HN oder SH;
    Z eine oder mehrere terminale funktionelle Gruppen darstellt, die ausgewählt werden aus Alkohol, Aldehyd, Carbonsäure, Organophosphonsäure, Thiol, Amin, Halogen, Cyano oder Silan, oder fehlend ist; und
    R1 und R2, unabhängig voneinander, ein gerader oder verzweigter gesättigter Wasserstoff oder Alkylradikal sind, der 1 bis 18 Kohlenstoffatome beinhaltet.
  2. Substrat nach Anspruch 2, dadurch gekennzeichnet, dass A einen gerad- oder verzweigtkettigen gesättigten oder ungesättigten Kohlenwasserstoff darstellt, der 16 Kohlenstoffatome umfasst.
  3. Substrat nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass A eine gesättigte Alkylgruppe und/oder eine gerade Alkylgruppe ist.
  4. Substrat nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Substrat aus Eisen, Nickel, Kobalt, Aluminium, Kupfer, Chrom, Titan, Zink, Gold, Silber, Ruthenium, Rhodium oder einer ihrer Legierungen besteht.
  5. Metallsubstrat nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass es sich um ein Flachprodukt handelt.
  6. Verfahren zur Herstellung eines Metallsubstrats nach einem der Ansprüche 1 bis 5, die folgenden Schritte umfassend:
    (i) Bereitstellung eines Metallsubstrats, das Hydroxylgruppen an der Oberfläche beinhaltet;
    (ii) in Kontakt bringen des Metallsubstrats mit einer Lösung von mindestens einer Organophosphorverbindung;
    wobei das Substrat nach der Behandlung gemäß dem Schritt (ii) nicht gespült wird.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass das zur Herstellung der Organophosphorverbindungslösung verwendete Lösungsmittel einen Alkohol und/oder Wasser umfasst.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass der Alkohol ausgewählt wird aus Methanol, Ethanol, Propanol, Isopropanol und Butanol.
  9. Verfahren nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, dass die Konzentration der Organophosphorverbindung in der Lösung mehr als 1 mM/l beträgt.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass die Organophosphorverbindungslösung übersättigt ist.
EP15770520.3A 2014-09-26 2015-09-25 Oberflächenbehandlung von metallsubstraten Active EP3198054B1 (de)

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FR1459158A FR3026412B1 (fr) 2014-09-26 2014-09-26 Traitement de surface de substrats metalliques
PCT/EP2015/072172 WO2016046401A1 (fr) 2014-09-26 2015-09-25 Traitement de surface de substrats métalliques

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US4048374A (en) * 1973-09-01 1977-09-13 Dynamit Nobel Aktiengesellschaft Functional organophosphonic acid esters as preservative adhesion promoting agents and coating for metals
US5103550A (en) * 1989-12-26 1992-04-14 Aluminum Company Of America Method of making a food or beverage container
WO1997018905A1 (en) * 1995-11-20 1997-05-29 Berg Technology, Inc. Method of providing corrosion protection
BR9713464A (pt) * 1996-08-30 2000-05-23 Solutia Inc Novos fluidos de usinagem de metal solúveis em água.
AU4695799A (en) * 1998-06-19 2000-01-05 Alcoa Inc. Method for inhibiting stains on aluminum product surfaces
ES2344371T3 (es) * 2006-01-09 2010-08-25 Basf Se Procedimiento para el tratamiento de superficies.
US9365931B2 (en) * 2006-12-01 2016-06-14 Kobe Steel, Ltd. Aluminum alloy with high seawater corrosion resistance and plate-fin heat exchanger
WO2009000820A2 (de) * 2007-06-28 2008-12-31 Siemens Aktiengesellschaft Korrosionsschützender zusatz für flüssigkeiten
TWI394863B (zh) * 2007-12-27 2013-05-01 Kansai Paint Co Ltd 金屬表面處理用組成物及從該金屬表面處理用組成物獲得之具有金屬表面處理層的表面處理金屬材
US8178004B2 (en) * 2008-06-27 2012-05-15 Aculon, Inc. Compositions for providing hydrophobic layers to metallic substrates

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FR3026412A1 (fr) 2016-04-01
CN107109657A (zh) 2017-08-29
EP3198054A1 (de) 2017-08-02
WO2016046401A1 (fr) 2016-03-31
CA2962057C (fr) 2021-04-20
US10196744B2 (en) 2019-02-05
PL3198054T3 (pl) 2024-01-08
FR3026412B1 (fr) 2019-03-29
CN107109657B (zh) 2019-08-30
ES2952509T3 (es) 2023-10-31
EP3198054C0 (de) 2023-06-07
US20180119287A1 (en) 2018-05-03
CA2962057A1 (fr) 2016-03-31

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