Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
  • C23F11/16—Sulfur-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • 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
  • C23F11/16—Sulfur-containing compounds
  • C23F11/165—Heterocyclic compounds containing sulfur as hetero atom

Definitions

• the subject of the present invention is a composition useful for temporarily protecting metal parts from corrosion, a process for preparing said composition and the metal parts coated with a dry film derived therefrom.
• the object of the present invention is precisely to propose a new water coating which complies with these requirements.
• a first approach consists in incorporating into coatings based on temporary protection oil formulations, one or more corrosion inhibitors.
• the corrosion inhibitors present in protective oils are chosen from amino compounds of the alcoholamine type, sulfonate derivatives such as their barium or sodium salts or al ylbenzenes sulfonates and acids of the holeic type.
• the present invention relates to a composition useful for imparting temporary protection against corrosion to metal surfaces
• a composition useful for imparting temporary protection against corrosion to metal surfaces comprising an oil-in-water emulsion characterized in that said emulsion comprises in its aqueous phase at least one compound of general formula I
• a C:, a haloalkyl group, C ⁇ ao with the halogen may be fluorine, chlorine, bromine or iodine, a Ci cvcioalkyle group G, a carboxvhque tonction or carboxvalkyle group G to G, n is an integer varying from 1 to 3 and
• X represents a sulfur or oxygen atom, in the form of one of its water-soluble salts
• the originality of the claimed composition is also based on the incorporation of a compound of general formula I in the aqueous phase and not in the lipid phase of the emulsion. implementation in the composition claimed Of a non-water-soluble nature, this compound is therefore present in the composition in a neutralized form with a view to giving it a satisfactory hydrosolubihte
• This neutralization of the compound or compounds of formula I, used according to the invention can be carried out in a conventional manner by a person skilled in the art. It can, for example, be obtained from ammonia, from morphohne. ethanolamine, ethanol or potash Depending on the reagent used, it may be necessary, if necessary, to adjust the pH of the final composition, to a value compatible with the recommended application, that is to say a a value between 8 2 in and 9> and preferably between 8.5 and 9 This can be easily achieved by adjusting the pH of the final emulsion by an additional addition of neutralizer such as ethanolanine for example
• the corrosion inhibitor of general formula I is preferably present in the claimed composition in an amount of 1 to 10 g / 1 and preferably from 1 1 to 3 g 1
• the emulsion can be defined as comprising, in dispersion in water, 3 to 13% by volume of an oily phase -s comprising from 75 to 90% by volume of at least one oil and 5 at 10% in olume of at least one surfactant If necessary, an additional corrosion inhibitor may be present at a rate of 5 to 15% by volume, in the oily phase
• the emulsion comprises, in dispersion in the aqueous phase, between approximately 3 and 8% and preferably approximately 6% by volume of an) oil
• the oil contained in the oily phase of the emulsion may consist of a mineral, vegetable or animal oil
• it is a mineral oil and preferably a paraffinic, naphtenic tvpe oil or a mixture of these ⁇
• mineral oil preferentially used according to the present invention mention will be made of any especially the soluble oil AQUASAFE 21 ⁇ .e C ⁇ STROL It is preferred to use as surfactant for the oily phase a surfactant of tvpe polvoxvethvlene
• a carboxv acid such as a barvum or sodium alkvl-sulfonate or an amine and fatty acid salt is advantageously used as an inhibitor of corrosion of the oily phase.
• the claimed composition comprises, as corrosion inhibitor, a water-soluble salt of benzothiazolvlthiosuccinic acid (ABTS) present at a concentration of between 1 and 3 g 1 and preferably of the order of 2.5 g / l in the aqueous phase of an emulsion at 6 ° o in soluble oil which is preferably oil AQUASAFE 213) from C ⁇ STROL
• ABTS benzothiazolvlthiosuccinic acid
• it is the ammonium salt of benzothiazol lthiosuccinic acid present at a concentration of around 2 5 g / 1
• the present invention also relates to a process for the preparation of said composition
• this process is characterized in that the compound or compounds of general formula I are incorporated in the form of an aqueous solution at the aqueous phase of the emulsion, prior to its emulsification with the oily phase
• the present invention also relates to a process for temporary protection against corrosion of metal parts.
• this process is characterized in that it comprises the steps consisting in applying to at least part of said metal part a composition according to the invention, and drying said coated metal part until a
• the composition according to the invention is applied to the surface of the metal part so as to saturate its absorption sites with compounds of general formula I and at the end of the heating of said composition, in order to obtain a film there is no compound of general formula I present in the thickness of the applied film
• ⁇ Processing is carried out in such a way as to saturate its adsorption sites with a compound of general formula I and to prevent the accumulation of this same compound of general formula I at the level of the thickness of the film.
• the adjustment of the optimal concentration of inhibitor of general formula I on the surface of the treated metal part can for example be appreciated and performs in the following manner, after having applied and dried on the surface of the 0 part a composition according to the invention of determined concentration in corrosion inhibitor (s) of general formula I
• the part is xiviated with 1 acetone, by quenching or by sprinkling Then, the saturation level of the adsorption sites on the surface is measured the metal part treated by performing an infrared spectrum of the hivivated part using the technique of ⁇ infrared spectroscopy to transform Fou ⁇ er (IRFT) under grazing incidence
• IRFT Fou ⁇ er
• aqueous composition according to the invention can of course be deposited in the form of a film on the surface of the metal parts to be protected by any suitable conventional oven, such as a coating device with a roller or the like or by spraying.
• a coating device with a roller or the like or by spraying.
• the part thus treated is then subjected drying in order to obtain a dry film according to the invention
• This heating may for example be accomplished by carrying the processed part has a temperature between ⁇ 0 and 100 ° C for a time varying between 1 ⁇ 20 seconds 10 minutes
• the present invention also relates to a metal part coated with a dry film for temporary protection against corrosion obtained from the claimed composition and / or in accordance with the claimed methods.
• the surface density of dry film on the surface of the 2o piece varies between 0 3 and 2 g / m " and more preferentially is of the order of 0 5 g / m "
• the term "metal parts” means movable thickness plates hot rolled thin sheets hot rolled cold rolled steel sheets as well as various kinds of steel plates and sheets, in particular bare steel.
• the metal parts coated with a dry protective film of composition as defined according to the invention prove to be resistant to corrosion and show good aptitude for stamping and sticking.
• the dry films obtained according to the claimed process show good adhesion properties with respect to various kinds of substrates on the surface of which they are capable of being applied to their surface
• the coatings derived from the claimed compositions have satisfactory and therefore advantageous performance in terms of stamping. This is how their character in terms of friction shows that they have a reduced coefficient of friction compared to conventional coatings.
• FIGS. 5 and 6 Characterization of the adsorption power of different inhibitors including ABTS
• the ABTS inhibitor is dissolved in an oily emulsion after neutralization with ammonia or with ethanolamine 2 ⁇
• an oily emulsion After neutralization and therefore dissolve 1 g of inhibitor in one liter of water , at least
• Irgacor L 184 Irgamet 42 from CIBA - Irgacor L 184
• inhibitors 1 to 5 are used to additivate an emulsion composed of a soluble mineral oil and water
• the mineral oil used is the soluble oil CASTROL AQUASAFE 21 ⁇
• the performance of the different compositions tested is assessed by applying them to pickled steel test pieces, polished with G600 paper in proportions such that the final grammage deposited on test pieces is of the order of 500 mg / m " (0 5 ⁇ m )
• the test piece is then immersed in an electrolytic mixture of demineralized water, 1% by weight of sodium chloride ( ⁇ aCl)
• the steel test piece is kept 30 min in the electrolyte in order to stabilize its electrochemical potential
• a potentiostat, a frequency converter of a reference electrode and a counter electrode a sinusoidal disturbance in potential is imposed on the test (in mV ) for different decreasing frequencies and we measure "response intensity" (in uA'cm " )
• test tubes are exposed to the atmosphere of 2 storage halls
• Ethanolamine neutralized ABTS inhibitor is introduced at concentrations varying between 0 5 and 20 g / 1 in the aqueous phase in a composition according to 1 invention comprising an aqueous emulsion based on 6% of oil C ASTROL AQU AS FE 2 1
• the corrosion resistances of the various corresponding compositions are determined by Humidotherm FKW according to the protocol described in equipment and method The results obtained are represented o on the graph of FIG. 1
• composition comprising 2> g 1 of ABTS inhibitor in neutralized form
• composition according to the invention comprising an ABTS concentration equal to 2 5 g / l (COMPOSITION 3) and with regard to the control compositions 1 2 and 4 identified more precisely in the chapter 'o Materials and Methods
• composition according to the invention that is to say composition 3 comprising a salt of AJBTS in an aqueous emulsion, exhibits a resistance which is significantly prolonged over time. Furthermore, the increase in resistance observed is clearly greater than that resulting from the superposition of the resistances induced respectively by the emulsion and by the ABTS considered isolation.
• compositions 1 2, 3 and 4 identified more precisely in the Materials and Methods chapter.
• This test consists in stacking test pieces previously coated with the solutions to be tested. The stacks are kept tight in order to simulate the contiguous turns of a steel coil or the stacked sheets of a pack of sheets.
• the stacked stack of specimens (“greenhouse pack”) is then introduced into a climatic chamber programmed to carry out alternating cycles of 32 h ("transport cycle”)
• composition 3 Only the metal part coated with a composition according to the invention, that is to say composition 3, exhibits a significantly improved corrosion resistance. This increase moreover reflects a difference between the emulsion and the ABTS salt.
• compositions 2 and 4 based on an aqueous solution respectively containing ABTS and an Irgacor L 184 / Irgamet 42 mixture, the compositions tested are always composed of Castrol AQUASAFE 21 soluble oil, diluted to 6% in water. demineralized (composition 1) and additive with different inhibitors (compositions 3 and 5 to 9)
• ABTS is present in an ammonia-neutralized form.
• the drying of emulsions 4 to 6 therefore leads to the evaporation of ammonia.
• composition 4 confers an advantageous behavior on the corresponding film compared to a film which has not undergone drying (composition 3). This effect is in fact linked to the implementation of ABTS neutralized with ammonia)
• the total resistances are determined by electrochemical impedance. performed according to the protocol described in the Material and Method chapter above.
• the single-pass friction tests are carried out in planar friction, with variable transverse pressure from 200 to 2,000 daN with high-speed steel tools, with an area of 1 cm 2 The speed of movement is 2 mm / s
• test pieces are cut from hot pickled sheets, grade BS2, in thickness of 2 mm
• Composition Has a protective oil used on the sheets as corrosion protection (QUAKER 8021) deposited at a rate of 2 gm "
• Composition B AQUASAFE 21 soluble oil at 6% in water deposited at a rate of 500 mg / m "
• Composition C Composition B additive of the organic inhibitor ABTS in salt form, (pH of the solution between 7.2 and 8 5) deposited at the rate of 500 mg / m "
• composition D identical to composition C, whose pH lo is stabilized between 8.5 and 9 by the addition of ethanolamine, deposited at the rate of
• composition A 1 ⁇
• measurements of wetting are carried out o of two compositions a composition based on an AQUASAFE 21 emulsion
• the test consists in depositing a drop of each of the emulsions on a steel test tube and in following the evolution of the contact angle of the drop (followed by spreading)
• the graph represents in figure 4 shows that a drop of emulsion
• AQUASAFE 21 additive by ABTS spreads much faster on steel than a drop of classic AQUASAFE 21 emulsion (WITNESS)
• WITNESS classic AQUASAFE 21 emulsion
• compositions comprise an emulsion having an oily base concentration of AQUASAFE 21 of 5% ! ⁇ T

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Paints Or Removers (AREA)

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• 1997
  • 1997-07-01 FR FR9708288A patent/FR2765595B1/fr not_active Expired - Fee Related
• 1998
  • 1998-06-23 JP JP2000501287A patent/JP4184595B2/ja not_active Expired - Fee Related
  • 1998-06-23 KR KR10-1999-7012620A patent/KR100522925B1/ko not_active Expired - Fee Related
  • 1998-06-23 EP EP98933689A patent/EP0996769B1/fr not_active Expired - Lifetime
  • 1998-06-23 US US09/446,887 patent/US6309697B1/en not_active Expired - Lifetime
  • 1998-06-23 DE DE69811900T patent/DE69811900T2/de not_active Expired - Lifetime
  • 1998-06-23 WO PCT/FR1998/001317 patent/WO1999001590A1/fr not_active Ceased
  • 1998-06-23 ES ES98933689T patent/ES2193544T3/es not_active Expired - Lifetime
  • 1998-06-23 AT AT98933689T patent/ATE233834T1/de active
  • 1998-06-23 CA CA002295864A patent/CA2295864C/fr not_active Expired - Fee Related

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