EP0996769B1 - Composition pour la protection temporaire contre la corrosion de pieces metalliques, ses procedes de preparation et d'application et pieces metalliques obtenues a partir de cette composition - Google Patents

Composition pour la protection temporaire contre la corrosion de pieces metalliques, ses procedes de preparation et d'application et pieces metalliques obtenues a partir de cette composition Download PDF

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Publication number
EP0996769B1
EP0996769B1 EP98933689A EP98933689A EP0996769B1 EP 0996769 B1 EP0996769 B1 EP 0996769B1 EP 98933689 A EP98933689 A EP 98933689A EP 98933689 A EP98933689 A EP 98933689A EP 0996769 B1 EP0996769 B1 EP 0996769B1
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EP
European Patent Office
Prior art keywords
composition
composition according
emulsion
general formula
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98933689A
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German (de)
English (en)
French (fr)
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EP0996769A1 (fr
Inventor
Lothaire Scherer
Ronald Kefferstein
Philippe Antoine
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sollac SA
Original Assignee
Sollac SA
Lorraine de Laminage Continu SA SOLLAC
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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
    • 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 protect metal parts from corrosion, a process for preparation of said composition and the metal parts coated with a dry film deriving from it
  • the object of the present invention is precisely to propose a new coating meeting these requirements
  • a first approach consists in incorporating into the coatings a based on temporary protection oil formulations, one or more inhibitors corrosion.
  • EP 129506 proposes the use of heterocyclic thioether of acids carboxylates related to those of the invention, as a corrosion inhibitor. However, these compounds are introduced directly into the oily phase of the corresponding emulsions.
  • This neutralization of the compound or compounds of formula I. used according to the invention can be carried out conventionally by a person skilled in the art. She can for example be obtained from ammonia, morpholine, ethanolamine, ethanol or potash. Depending on the reagent used, it may be, if necessary necessary to adjust the pH of the final composition, to a value compatible with the recommended application, i.e. at a value between 8.2 and 9.5 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 / l and preferably 1 at 3.5 g / l.
  • ABTS benzothiazolylthiosuccinique
  • the emulsion can be defined as comprising in dispersion in water, 3 to 13% by volume of an oily phase comprising from 75 to 90% by volume of at least one oil and from 5 to 10% by volume at least one surfactant If applicable, 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 phase aqueous, between about 3 and 8% and preferably about 6% by volume of a oil.
  • the oil contained in the oily phase of the emulsion can be consisting of mineral, vegetable or animal oil.
  • it is a mineral oil and preferably a paraffinic, naphthenic type oil or a mixture thereof.
  • mineral oil preferably used according to the present invention, particular mention will be made of the soluble oil AQUASAFE 21® from CASTROL.
  • surfactant for the oily phase a polyoxyethylene type surfactant.
  • the corrosion inhibitor used is oily phase, a carboxylic acid, a sodium or barium alkyl sulfonate or an amine and fatty acid salt.
  • the composition claimed includes a water-soluble salt of the acid as a corrosion inhibitor benzothiazolylthiosuccinique (ABTS), present, at a concentration between 1 and 3.5 g / l and preferably of the order of 2.5 g / l, in the aqueous phase of a 6% emulsion in soluble oil which is preferably AQUASAFE 21® oil from CASTROL.
  • ABTS benzothiazolylthiosuccinique
  • it is the ammonium salt of the acid benzothiazolylthiosuccinic present at a concentration of the order of 2.5 g / l.
  • the present invention also relates to a method of preparation of said composition.
  • this process is characterized in that the one or more compounds of general formula I are incorporated in the form of a solution aqueous at the aqueous phase of the emulsion, prior to its emulsification with the oily phase.
  • the present invention also relates to a method of temporary protection against corrosion of metal parts
  • the composition according to the invention is applied to the surface of the metal part so as to saturate its absorption sites for compounds of general formula I and that after heating said composition, in order to obtain a film thereof, no compound of general formula I present in the thickness of the applied film.
  • the performance of the coating film is indeed clearly improved if the application of the composition claimed on the metal plate to process is carried out so as to saturate its adsorption sites with a compound of general formula I and to prevent the accumulation of this same compound of formula general I in terms of film thickness.
  • Adjusting the optimal concentration of formula inhibitor general I on the surface of the metal part to be treated can for example be appreciated and performed as follows, after applying and drying on the surface of the exhibits a composition according to the invention, of determined concentration corrosion inhibitor (s) of general formula I.
  • the leaching of the acetone, dip or spray piece Then, we measure the level of saturation of the adsorption sites on the surface of the treated metal part performing an infrared spectrum of the leached room, using the technique of Fourier infrared transform spectroscopy (IRFT) under grazing incidence at 80 °
  • IRFT Fourier infrared transform spectroscopy
  • aqueous composition according to the invention can be clearly understood deposited in the form of a film, on the surface of the metal parts to be protected, by any suitable conventional means such as a roller coating device or similar or by spraying.
  • the part thus treated then undergoes a drying in order to obtain a dry film, in accordance with the invention
  • This heating can be, for example, carried out by wearing the part treated at a temperature between 50 and 100 ° C for a varying time between about 20 seconds to 10 minutes.
  • the present invention also relates to a metal part coated with a dry film for temporary protection against corrosion obtained from the composition claimed and / or in accordance with the claimed processes
  • the surface density of dry film on the surface of the part varies between 0.3 and 2 g / m 3 and more preferably is of the order of 0.5 g / m 2
  • the term "metal parts" is used. of the hot-rolled medium thickness plates, thin-rolled sheets hot, cold rolled steel sheets as well as various kinds of plates and sheets steel, especially bare steel.
  • the coatings derived from the claimed compositions have satisfactory tribological performances and therefore advantageous stamping level. This is how their characterization in terms of friction shows that they have a reduced coefficient of friction compared to conventional coatings.
  • compositions according to the invention can also be applied effectively on metal plates already coated with a dry film, and are found therefore particularly advantageous for treating turns and outer edges of coil already coated with a non-greasy coating or to protect parts pickled metal.
  • the mineral oil used is CASTROL soluble oil AQUASAFE 21®
  • This soluble oil is diluted to 6% in demineralized water and the pH of the emulsion thus obtained is 9.2
  • compositions were in Table I below Composition Typical concentration 1 (soluble oil) Typical concentration 2 (inhibitor (s)) -1- CASTROL AQUASAFE 21 emulsion (soluble oil only) 6% 0 (60 g / l) -2- (ABTS) (inhibitor only) 0 aqueous solution 30 g / l -3- composition 1 + composition 2 6% 2.5 g / l (60 g / l) -4- IrgacorL184 + Irgamet 42 0 30 g / l (L 184) and 1.5 g / l (142) -5- composition 1 + composition 4 6% 30 g / l (L 184) and 1.5 g / l (142) (60 g / l) -6- composition 1 + PX2881 6% 15 ml / l (60g / l) -7- composition 1 + PX2881 6% 5 ml / l (60g / l)
  • the performance of the different compositions tested is assessed by applying them to pickled steel specimens, polished with G600 paper, in proportions such that the final grammage deposited on specimens is of the order of 500 mg / m 2 (0.5 ⁇ m) .
  • the test piece is then immersed in an electrolyte composed of demineralized water, of 1% by weight of sodium chloride (NaCl).
  • the steel test piece is kept 30 minutes in the electrolyte in order to stabilize its electrochemical potential. After 30 min, using a potentiostat, a frequency analyzer, a reference electrode and a counter electrode, a sinusoidal potential disturbance (in mV) is imposed on the test piece.
  • different decreasing frequencies and we measure "response intensity" in ⁇ A / cm 2 )
  • the thickness of the films applied is 0.5 g / m 2 on average (0.5 ⁇ m).
  • the composition is always composed of Castrol AQUASAFE soluble oil. 21, diluted to 6% in demineralized water
  • ABTS inhibitor neutralized with ethanolamine, is introduced at concentrations varying between 0.5 and 20 g / l in the aqueous phase, in a composition according to the invention comprising an aqueous emulsion based on 6% of CASTROL AQUASAFE 21
  • the corrosion resistance of the different corresponding compositions are determined by FKW humidifier according to the protocol described in material and method The results obtained are represented on the graph of figure 1
  • composition comprising 2.5 g / l of ABTS inhibitor in neutralized form
  • composition according to the invention comprising a ABTS concentration equal to 2.5 g / l (COMPOSITION 3) and with regard to control compositions 1, 2 and 4, identified more precisely in the chapter Materials and methods.
  • compositions undergo the EB hall and finishing hall tests whose protocols are explained in Materials and Methods.
  • composition Number of days before corrosion appears (hall EB1) Number of days before corrosion appears (finishing hall) 1 15 to 25 days 66 days 2 2 to 6 days 15 days 3 30 to 65 days 110 days 4 3 days / 5 10 to 20 days /
  • composition according to the invention that is to say the composition 3 comprising an ABTS salt in an aqueous emulsion
  • present resistance significantly extended over time What is more, the increase in resistance observed is clearly greater than that resulting from superimposition of the resistances induced respectively by the emulsion and by the ABTS.
  • compositions 1,2, 3 and 4 identified more specifically in the Materials and Methods chapter
  • This test consists of stacking previously coated test pieces by the solutions to be tested.
  • the batteries are kept tight to simulate the turns contiguous with a steel coil or the stacked sheets of a bundle of sheets.
  • the stacked stack of test pieces (“tight packet") is then introduced into a climatic chamber programmed to alternate 32 hr cycles ("transport cycle").
  • compositions Number of cycles before corrosion appears 1 ⁇ 6 cycles 2 ⁇ 6 cycles 3 > 19 cycles 4 ⁇ 6 cycles 5 ⁇ 6 cycles
  • composition 3 exhibits corrosion resistance significantly improved This increase also reflects a synergy between the emulsion and the ABTS salt.
  • compositions 2 and 4 based on an aqueous solution containing ABTS and an Irgacor L184 / Irgamet 42 mixture respectively, tested compositions are always composed of Castrol AQUASAFE soluble oil 21, diluted to 6% in demineralized water (composition 1) and added with different inhibitors (compositions 3 and 5 to 9)
  • ABTS is present in a form neutralized with ammonia.
  • the drying of emulsions 4 to 6 therefore leads to a evaporation of ammonia.
  • composition 4 the completion of a step of drying (composition 4) gives an advantageous behavior to the film corresponding to a film which has not undergone drying (composition 3) This effect is in fact linked to the implementation of ammonia-neutralized ABTS
  • Total resistances are determined by impedance electrochemical. performed according to the protocol described in the Hardware chapter and Previous method
  • the single-pass friction tests are carried out in plane-plane friction, at 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 A The friction curves improve with compositions C and D The results obtained are better than with a protective oil, having stamping properties (composition A)
  • wettability measurements are carried out of two compositions, a composition based on an AQUASAFE 21 emulsion (WITNESS) and a composition based on an additive AQUASAFE 21 emulsion by ABTS (ABTS) at a concentration of 2.5 g / l, in the form of its salt neutralized and at pH around 8.5 to 9
  • WITNESS AQUASAFE 21 emulsion
  • ABTS additive AQUASAFE 21 emulsion by ABTS
  • the test consists in depositing a drop of each of the emulsions on a steel test piece and to follow the evolution of the contact angle of the drop (follow-up sprawl)
  • compositions tested comprise an emulsion having an oily base concentration of AQUASAFE 21 of 5% Composition Concentration in ABTS ABTS dissolved in: pH of emulsions AT 0.25% oil 9.7 B 0.125% oil 10.1 VS 0.25% emulsion 9 D 0.75% emulsion 8.9 E 3.75% emulsion 10.2

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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)
EP98933689A 1997-07-01 1998-06-23 Composition pour la protection temporaire contre la corrosion de pieces metalliques, ses procedes de preparation et d'application et pieces metalliques obtenues a partir de cette composition Expired - Lifetime EP0996769B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9708288 1997-07-01
FR9708288A FR2765595B1 (fr) 1997-07-01 1997-07-01 Composition pour protection temporaire contre la corrosion de pieces metalliques, ses procedes de preparation et d'application et pieces metalliques obtenues a partir de cette composition
PCT/FR1998/001317 WO1999001590A1 (fr) 1997-07-01 1998-06-23 Composition pour protection temporaire contre la corrosion de pieces metalliques, ses procedes de preparation et d'application et pieces metalliques obtenues a partir de cette composition

Publications (2)

Publication Number Publication Date
EP0996769A1 EP0996769A1 (fr) 2000-05-03
EP0996769B1 true EP0996769B1 (fr) 2003-03-05

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EP98933689A Expired - Lifetime EP0996769B1 (fr) 1997-07-01 1998-06-23 Composition pour la protection temporaire contre la corrosion de pieces metalliques, ses procedes de preparation et d'application et pieces metalliques obtenues a partir de cette composition

Country Status (10)

Country Link
US (1) US6309697B1 (enExample)
EP (1) EP0996769B1 (enExample)
JP (1) JP4184595B2 (enExample)
KR (1) KR100522925B1 (enExample)
AT (1) ATE233834T1 (enExample)
CA (1) CA2295864C (enExample)
DE (1) DE69811900T2 (enExample)
ES (1) ES2193544T3 (enExample)
FR (1) FR2765595B1 (enExample)
WO (1) WO1999001590A1 (enExample)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2956520B1 (de) * 2013-02-13 2019-11-06 Basf Se Gefrierschutzmittel-konzentrat mit korrosionsschutz und daraus hergestellte wässrige kühlmittelzusammensetzung
IN2013KO01135A (enExample) * 2013-10-01 2015-04-10 Tata Steel Ltd
CN106609371B (zh) * 2015-10-27 2019-04-16 中国石油化工股份有限公司 一种缓蚀剂及其制备方法和应用
KR102045640B1 (ko) * 2017-12-22 2019-11-15 주식회사 포스코 방청 조성물, 금속 기재의 방청처리 방법 및 방청 코팅층을 포함하는 금속재

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2218557A (en) * 1939-05-12 1940-10-22 Agnes J Reeves Greer Treatment of metals
GB1028924A (en) * 1962-03-13 1966-05-11 Castrol Ltd Lubricating compositions containing heterocyclic thio-ethers of saturated carboxylic acids
GB1104755A (en) * 1964-06-10 1968-02-28 Ici Ltd De-watering of metal surfaces
SE401693B (sv) * 1975-09-24 1978-05-22 Berol Kemi Ab Temporert korrosionsskyddande oljeemulsion
GB8313321D0 (en) * 1983-05-14 1983-06-22 Ciba Geigy Ag Preparation of mercaptan substituted carboxylic acids
US5347008A (en) * 1983-05-14 1994-09-13 Ciba-Geigy Corporation Thio(cyclo) alkanepolycarboxylic acids containing heterocyclic substituents
GB8313322D0 (en) * 1983-05-14 1983-06-22 Ciba Geigy Ag Heterocyclic-(cyclo)aliphatic carboxylic acids
DE3341633A1 (de) * 1983-11-17 1985-05-30 Sanshin Kagaku Kogyo Co., Ltd., Yanai, Yamaguchi Rosthemmende substanz
GB8412064D0 (en) * 1984-05-11 1984-06-20 Ciba Geigy Ag Compositions containing heterocyclic corrosion inhibitors
IT1185511B (it) * 1985-02-19 1987-11-12 Hoechst Italia Agenti anticorrosivi acquosi contenenti un sale ammonico dell'acido 2-benzotiazoliltiocarbossilico
JPS62136580A (ja) * 1985-12-10 1987-06-19 Sanshin Kagaku Kogyo Kk アルミニウム及びアルミニウム合金の腐食抑制剤
DE3933137A1 (de) * 1989-10-04 1991-04-18 Henkel Kgaa Verfahren zur herstellung stabiler, niedrig-viskoser o/w-rostschutzemulsionen
FR2692912B1 (fr) * 1992-06-30 1995-06-30 Lorraine Laminage Procede de protection contre la corrosion de pieces metalliques et pieces metalliques obtenues par ce procede.

Also Published As

Publication number Publication date
FR2765595A1 (fr) 1999-01-08
FR2765595B1 (fr) 1999-10-01
ATE233834T1 (de) 2003-03-15
CA2295864C (fr) 2008-04-08
US6309697B1 (en) 2001-10-30
CA2295864A1 (fr) 1999-01-14
EP0996769A1 (fr) 2000-05-03
JP2001509542A (ja) 2001-07-24
WO1999001590A1 (fr) 1999-01-14
JP4184595B2 (ja) 2008-11-19
DE69811900D1 (de) 2003-04-10
KR100522925B1 (ko) 2005-10-19
DE69811900T2 (de) 2004-02-12
ES2193544T3 (es) 2003-11-01
KR20010020606A (ko) 2001-03-15

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