EP0765952A1 - Verfahren zur Vorbehandlung der metallischen Oberfläche eines Gegenstandes, insbesondere ein Stahl-Blech, für die direkte Emaillierung - Google Patents

Verfahren zur Vorbehandlung der metallischen Oberfläche eines Gegenstandes, insbesondere ein Stahl-Blech, für die direkte Emaillierung Download PDF

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Publication number
EP0765952A1
EP0765952A1 EP96401848A EP96401848A EP0765952A1 EP 0765952 A1 EP0765952 A1 EP 0765952A1 EP 96401848 A EP96401848 A EP 96401848A EP 96401848 A EP96401848 A EP 96401848A EP 0765952 A1 EP0765952 A1 EP 0765952A1
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Prior art keywords
sheet
pickling
phosphating
nickel
treatment
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EP96401848A
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English (en)
French (fr)
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EP0765952B1 (de
Inventor
Louis Guillot
Vincent Cholet
Daniel Vonner
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Sollac SA
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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
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/42—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 molybdates, tungstates or vanadates containing also phosphates
    • 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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • 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
    • C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
    • C23D3/00—Chemical treatment of the metal surfaces prior to coating

Definitions

  • the invention relates to a process for preparing metal surfaces for enamelling, in particular sheet steel.
  • the mass enamel layer serves as a bonding layer to the sheet.
  • the cover layer is the top layer.
  • the metal surface to be enameled is prepared in order to obtain, in particular, good adhesion of the enamel layer to the sheet.
  • a metal surface for direct enameling a first process is known in which the metal surface is etched and then the surface is treated with a sulphate solution containing nickel as a layer-forming cation; this surface treatment is also called "nickel plating".
  • Pickling and surface treatment are generally carried out by immersion or by spraying.
  • the disadvantage of this first method is that it requires a deep pickling, corresponding to a removal of material greater than 15 g / m2 on the surface to be enameled, to obtain enamels having satisfactory qualities in terms of adhesion and surface appearance.
  • the removal of necessary material is commonly of the order of 25 g / m2 of surface to be glazed.
  • This deep pickling is a drawback insofar as it generates very large volumes of sludge to be treated.
  • document FR 2 593 522 proposes to replace the pickling and sulphate treatment by phosphating using a solution containing essentially nickel as a layer-forming cation; but the adhesion of the enamel has proved to be very insufficient in this case, and in any case less than that obtained in the case of the first process mentioned.
  • the treatment effluents then contain heavy metals, in particular molybdenum, and can be expensive to treat.
  • the object of the invention is to obtain, on the metallic surface of an object, an enamel of strong adhesion and of good surface appearance by a preparation of the sheet metal generating less bulky effluents and easier to treat.
  • the subject of the invention is a process for preparing the metal surface of an object, in particular made of sheet steel, for enamelling in direct mode, in which the surface is scoured and then treated, characterized in that the etched surface is treated in two stages, a first stage of so-called “amorphous" phosphating treatment suitable for forming a layer of at least 0.2 g / m2 on said surface, then a second stage of treatment known as " nickel plating ".
  • Strong acids are preferably used for pickling, which makes it possible to reduce the pickling time.
  • a phosphate solution forming a layer is therefore used; this treatment is known in itself, in particular for the preparation of a sheet for stamping.
  • the nickel-plating treatment is known in itself for the preparation of a surface for direct enameling after a deep pickling and corresponds for example to the treatment of the first method of the prior art described above.
  • the nickel-plating conditions are fixed in order to obtain a deposit of between 0.5 and 2.5 g / m2 on the surface to be glazed.
  • the surface treatment according to the invention which comprises two stages, one of amorphous phosphating, the other of nickel plating, it is found that a light pickling is sufficient to obtain a reproducible enamel at a time strongly adherent and having a satisfactory surface appearance.
  • Light stripping means a stripping corresponding to a material removal of at most 15 g / m2, when the surface to be stripped is made of sheet steel.
  • the quantity of sludge to be treated is therefore limited, the presence of heavy metals in the surface treatment effluents is avoided, while obtaining in direct mode a layer of enamel as adherent as by the first process cited.
  • the prior art namely a deep pickling followed by a single nickel-plating treatment with a sulphate solution.
  • the shaping for example by stamping, is deemed to destroy the surface preparation for direct enameling, it is even shaped before the preparation of the surface; for, a sheet which, in the reverse order, would be pickled and then shaped (including oiling and degreasing) no longer had sufficient surface reactivity to make the surface treatment effective.
  • the invention also aims to simplify the method of manufacturing an object in enamelled sheet.
  • the invention therefore also relates to a method of manufacturing an object made of enameled metal sheet in direct mode, which comprises a shaping operation, a preparation of the surface according to the invention, and an operation enameling, characterized in that the shaping operation is carried out after pickling and after the first stage of surface treatment called amorphous phosphating.
  • the etched and then phosphated surface nevertheless retains sufficient reactivity after shaping to make the nickel-plating treatment effective and give the enamel good adhesion and a good appearance. of surface.
  • This new order of manufacturing operations also brings an additional advantage in terms of shaping since, thanks to the prior phosphating, the tribological properties of the surface are significantly improved, and therefore the lubrication between the sheet and the shaping tools. form.
  • this new order of manufacturing operations makes it possible to supply already pickled and phosphated sheets, suitable for direct enameling after possible shaping and a simple nickel-plating treatment; for its part, the enameler no longer needs pickling facilities and is freed from the treatment of pickling sludge.
  • FIG. 1 represents the adhesion of layers of enamel for two different surface preparations and as a function (abscissa axis) of the quantity of material removed during the prior pickling (g / m2 / face).
  • a metallic object to be enameled is taken.
  • This object is produced by shaping a sheet metal blank, here of steel. According to the invention, the sheet is etched then a first amorphous phosphating surface treatment is carried out.
  • composition of the pickling bath is known in itself; to shorten the pickling time, preferably using baths based on strong acid, for example sulfuric acid.
  • the pickling conditions are chosen so as to remove at most 15 g / m2 of steel (per side).
  • the amorphous phosphating bath is known in itself.
  • the phosphating conditions are chosen to deposit a layer of at least 0.2 g / m2 per side on the sheet to be glazed.
  • a phosphating solution and suitable application conditions are chosen so that the weight of the layer does not exceed 2 g / m2 per side.
  • a suitable phosphating solution is chosen to obtain a layer based on amorphous phosphate of sodium, calcium and iron.
  • the phosphating solution used does not contain heavy metals, nor does the phosphating effluent contain it.
  • the second surface treatment of the preparation process according to the invention is then carried out.
  • This treatment is of a conventional type of nickel plating with a solution containing nickel cations, known in itself for preparing a metal surface for direct enameling.
  • the solution contains, for example, sulphate or phosphite anions.
  • the nickel-plating conditions are adapted in a manner known per se to obtain a deposit of 0.5 to 2.5 g / m2 on the surface of the object to be enamelled.
  • the nickel-plating effluents are those which are usually found upstream of the direct enameling installations of the prior art and do not pose any particular problem for their treatment; an advantage of the invention is that they do not contain heavy metals.
  • the object is coated with a single layer of covered enamel which is cooked in a manner known per se.
  • an enamel layer is obtained having a strong adhesion and a good surface appearance.
  • Light stripping means a stripping corresponding to a material removal of at most 15 g / m2 if the surface of the object to be glazed is made of steel.
  • strong adhesion is meant an adhesion at least comparable to that which would be obtained by preparing the surface of the object according to the first process cited in the prior art; this process differs essentially from that of the invention by a greater stripping and by the absence of the phosphating treatment.
  • a quantity of pickling sludge is also generated which is much lower than that of the first process cited in the prior art; the quantity of sludge can in particular be reduced by 40%.
  • the surface treatment effluents do not contain heavy metals, unlike the third process cited in the prior art, using treatment solutions containing molybdenum.
  • the invention can also be implemented in the context of a method for manufacturing an object in enamelled sheet in direct mode.
  • the sheet metal strip is stripped and then a first amorphous phosphating surface treatment is carried out.
  • the pickling and the phosphating treatment are carried out online after work hardening, at a high rate, for example at a speed of 30 m / min. ; pickling time can be significantly reduced compared to the pickling times of the preparation processes of the prior art: for example 2 to 25 seconds compared to commonly more than five minutes in the prior art.
  • pickling conditions are chosen in a manner known per se to obtain strong adhesion of the enamel while removing at most 15 g / m2 per side.
  • An amorphous phosphating bath known in itself is used, such as the bath commercially known as Bonderite 901 from the company PARKER, at a temperature of approximately 60 ° C.
  • the pickling sludge and the phosphating effluents can be treated in effluent treatment installations provided elsewhere for treating the rolling and work hardening effluents.
  • the pickled and phosphated sheet can be wound and sent to the enamellers, who carry out the shaping and enameling directly after simple nickel plating.
  • the pickled and phosphated sheet can then be considered as an intermediate commercial product, prepared for direct enameling.
  • the phosphating treatment provides temporary protection against corrosion and prepares for shaping.
  • the shaping is therefore then carried out, before the second nickel-type surface treatment.
  • the sheet is oiled, it is shaped, in particular by stamping, and the part formed is degreased, for example in an alkaline solution.
  • the coefficient of friction of the treated sheet against the forming tools is lower than with an untreated sheet, which facilitates the operation of shaping.
  • the second surface treatment of the preparation process according to the invention is then carried out as before, that is to say nickel plating.
  • the shaped and nickel-plated sheet is now ready for direct enameling.
  • the sheet is coated with a single layer of covered enamel which is fired in a manner known per se: the object is then obtained in enameled sheet.
  • an enamel layer is obtained having an adhesion entirely comparable to that obtained in the first embodiment; this result indicates that, even after shaping, the etched and phosphated surface remained sufficiently reactive to make the nickel-plating treatment effective.
  • part of the surface preparation treatment, in particular pickling is advantageously displaced before shaping: pickling can then be carried out continuously on the sheet metal strip directly downstream of the rolling, on large capacity industrial installations which benefit from widely dimensioned effluent and sludge treatment installations.
  • the amorphous phosphating treatment which is an integral part of the preparation for enameling, facilitates shaping.
  • composition of treatment solutions and deposits made on the surface of steel sheets is indicated; the analysis methods used to obtain these compositions are: chromatonionic analysis, atomic absorption and analysis by inductively coupled plasma for solution analyzes, as for deposit analyzes which are carried out after re-solution.
  • the purpose of this example is to illustrate the first method cited in the prior art in which a deep pickling is carried out followed by a single nickel-plating treatment of the metal surface to be glazed.
  • the sheet to be enamelled is a sheet of decarburized steel 1 mm thick, called SOLFER from the company SOLLAC.
  • the sheet is shaped, then degreased in an alkaline solution.
  • the sheet is then pickled by immersion for 6 to 11 minutes in an acid solution at approximately 70 ° C. containing approximately 70 g / l of sulfuric acid.
  • the pickling time is adjusted to obtain a weight loss of the sheet from 20 to 40 g / m2 per side.
  • This weight loss is necessary to obtain the qualities of adhesion and surface appearance of the enamel to be deposited.
  • This stripping generates sludge to be treated; the amount of sludge generated is proportional to the target weight loss.
  • the etched surface is then treated by immersion for 3 to 6 minutes in a nickel-plating solution at approximately 70 ° C. containing approximately 11 g / l of nickel sulphate, the pH of which has been adjusted to approximately 2.8 by addition of sulfuric acid. .
  • the nickel-plating time is adjusted to obtain a nickel-plating deposit of between 0.5 and 2.5 g / m2 per side.
  • the coated surface is then coated with enamel.
  • the enamel is then baked under conditions specific to its composition, here about 3 minutes at around 820 ° c.
  • the adhesion of the enamel layer to the sheet steel substrate is evaluated according to standard EN 10209, which defines a scale of five ratings, from the value 1 for excellent adhesion to the value 5 for poor adhesion.
  • a person skilled in the art evaluates the surface quality in a manner known per se, in particular by visually verifying the absence of defects such as bites, broths, nail blows.
  • the enamel obtained has a level of adhesion of 1 and a surface appearance qualified as good.
  • the purpose of this example is to illustrate the third method cited in the prior art in which a light pickling is carried out followed by a single treatment of the metal surface to be enameled with a phosphating solution containing nickel and molybdenum.
  • the sheet is then pickled by immersion for 4 to 12 minutes in an acid solution at approximately 65 ° C. containing approximately 25 g / l of sulfuric acid.
  • the pickling time is adjusted to obtain a weight loss of the sheet from 5 to 15 g / m2 per side.
  • the loss of weight on pickling can be approximately 50% less than that of Comparative Example 1 and the quantity of sludge generated by pickling is reduced in the same proportions.
  • the etched surface is then treated by immersion for 6 to 12 minutes in a phosphating solution at approximately 60 ° C.
  • the phosphating solution is commercially available under the name VP 10091 from the company CHEMETALL.
  • the treatment time is adjusted to obtain a deposit of between 1 and 1.5 g / m2 per side.
  • the phosphating solution here contains heavy metals, in particular molybdenum, and generates effluents which can be expensive to treat.
  • the deposit obtained typically contains the following elements: P2O5: 0.1 to 0.2 g / m2 / side - Na: 0.05 to 0.1 g / m2 / side - Ni: 0.05 to 0.1 g / m2 / side - Mo: 0.05 to 0.1 g / m2 / side - Ca: 0.05 to 0.1 g / m2 / side.
  • the molybdenum / nickel proportion is much higher in the deposit than in the treatment solution, which indicates that the molybdenum deposits preferentially over nickel; thus, the proportion of nickel deposited remains lower than that of Comparative Example 1.
  • this method does not make it possible to achieve the same level of adhesion as the first method cited in the prior art (cf. comparative example 1).
  • the purpose of this example is to illustrate the surface preparation process according to the invention.
  • the sheet is then pickled by immersion for 1.5 to 4.5 minutes in an acid solution at approximately 70 ° C. containing approximately 70 g / l of sulfuric acid.
  • the pickling time is adjusted to obtain a weight loss of the sheet from 5 to 15 g / m2 per side, with the same advantage in terms of the amount of sludge generated as in Comparative Example 2.
  • the etched surface is then treated by immersion for 0.5 to 6 minutes in a phosphating solution at approximately 60 ° C.
  • the phosphating solution is commercially available under the name Bonderite 901 from the company PARKER.
  • This solution mainly contains the following elements: P2O5: 5 to 15 g / l - sodium: 10 to 20 g / l - nitrates (expressed as NO3-): 0 to 4 g / l - calcium: 5 to 20 g / l - and, for the elements Ni, Mo, Si, Fe, SO4, F: ⁇ 0.05 g / l.
  • the treatment time is adjusted to obtain a deposit of between 0.2 and 2 g / m2 per side.
  • the deposit obtained typically has the following elements: P2O5: 0.02 to 0.5 g / m2 / side - Na: 0.02 to 0.1 g / m2 / side - Ca: 0.2 to 0.5 g / m2 / face; the nickel and molybdenum contents are not measurable and are less than 0.005 g / m2 / side.
  • the phosphated surface is then treated by immersion for 3 to 6 minutes in a nickel-plating solution as in Comparative Example No. 1.
  • the level of adhesion is comparable to that of Comparative Example 1, that is to say that obtained with the first process cited in the prior art.
  • the purpose of this example is to illustrate the process for manufacturing an object made of enamelled sheet metal according to the invention, in which it is shaped after pickling, in particular after the phosphating treatment and before the nickel-plating treatment.
  • the sheet is then etched by immersion for 5 to 15 seconds in an acid solution at approximately 100 ° C. containing 750 g / l of sulfuric acid approximately.
  • the pickling time is adjusted to obtain a weight loss of the sheet from 5 to 15 g / m2 per side, with the same advantage in terms of the amount of sludge generated as in Comparative Example 2.
  • the pickled surface is then treated by immersion for 5 to 25 seconds in the same phosphating solution as in Example 1, at approximately 60 ° C.
  • the phosphating time is adjusted to obtain a deposit of between 0.2 and 2 g / m2 / face having the same composition approximately.
  • the phosphated sheet is then shaped to form an object, according to a conventional sequence comprising an oiling of the sheet, the shaping proper and an alkaline degreasing.
  • the shaping is facilitated by the prior phosphating treatment: there is indeed a decrease in the coefficient of friction compared to that which would be observed with the same oil on the same sheet. , raw or coming directly from pickling.
  • the metal surface of the object is then treated by immersion for 3 to 6 minutes in a nickel-plating solution as in Comparative Example No. 1.
  • the level of adhesion and the surface appearance are comparable to those of Example 1, which indicates that the shaping did not deteriorate the surface reactivity obtained during pickling, although carried out after pickling.
  • Example 1 the advantages already mentioned in Example 1 are added to the possibility of carrying out the first stages of surface preparation, namely pickling and phosphating, on high-speed industrial lines, in particular directly at the exit from rolling. , more precisely of work hardening.
  • the shaping is also facilitated.
  • the purpose of this example is to illustrate, in the surface preparation process according to the invention, the importance of the amorphous phosphating step for obtaining good adhesion, when only a light pickling is carried out beforehand. not more than about 15 g / m2 / side.
  • the curve in FIG. 1 represents the adhesion results obtained for the two series of samples (on the ordinate: 1 for very good adhesion, 5 for poor adhesion) as a function of the amount of material removed during pickling (on the abscissa). : 0 to 25 g / m2 / side).
  • the curve marked with squares - "phosphated” - corresponds to the samples prepared according to the invention
  • the curve marked with diamonds - "not phosphated” - corresponds to the samples prepared according to the prior art with simple nickel plating after pickling.
  • FIG. 1 clearly shows that there are significant differences in adhesion between the two surface preparation processes, as soon as the pickling is less than or equal to 20 g / m2 / face, in particular when it is at more than 15 g / m2 / side.
  • FIG. 1 also shows that in order to obtain sufficient adhesion of the enamel layer when proceeding according to the invention, it is advisable for the preliminary stripping to be preferably greater than or equal to 5 g / m2 / face: the level of adhesion is then 3; to obtain the same level of adhesion by proceeding without amorphous phosphating, the surface should be stripped at least at the level of 15 g / m2 / face.
  • the purpose of this example is to show that the etched and phosphated surface retains, after shaping, sufficient reactivity to make effective a direct nickel-plating treatment and to obtain good adhesion of the enamel layer.
  • the operation of shaping a sheet consists of oiling it, deforming it, in particular by stamping, and finally degreasing it.
  • Unprocessed steel is called untreated raw steel.
  • Protective oil is an oil usually used for temporary protection against corrosion, in particular for the storage of sheets.
  • Stamping oil is an oil usually used for stamping operations, suitable for improving the tribological properties of a sheet surface.
  • the tribological properties of the surfaces of the different samples are measured in the following manner, all the samples having the same dimensions.
  • the sample to be measured is clamped in a blank greenhouse with a predetermined clamping force F s .
  • the tribological properties are characterized by then measuring the maximum drawing force F d of the sheet in the blank holder.
  • This maximum drawing force F d is obviously proportional to the clamping force F s .
  • Maintaining the surface reactivity in the event of friction is illustrated below in the example.
  • an M2 or M4 type sample (see above) is shaped by stamping.
  • the "rubbed" areas are areas where the surface has been substantially modified by friction on the stamping tool, where therefore the surface reactivity may have been degraded.
  • non-rubbed areas are areas which do not seem to have undergone particular friction and which have retained the appearance they had before shaping.
  • the shaping therefore does not degrade the surface reactivity, which makes it possible, according to the invention, to nickel directly after the shaping, without repeating stripping.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • ing And Chemical Polishing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP96401848A 1995-09-28 1996-08-29 Verfahren zur Vorbehandlung der metallischen Oberfläche eines Gegenstandes aus Stahl-Blech für die direkte Emaillierung Expired - Lifetime EP0765952B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9511376 1995-09-28
FR9511376A FR2739396B1 (fr) 1995-09-28 1995-09-28 Procede de preparation de la surface metallique d'un objet, notamment en tole d'acier, pour emaillage en mode direct

Publications (2)

Publication Number Publication Date
EP0765952A1 true EP0765952A1 (de) 1997-04-02
EP0765952B1 EP0765952B1 (de) 2001-07-18

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EP96401848A Expired - Lifetime EP0765952B1 (de) 1995-09-28 1996-08-29 Verfahren zur Vorbehandlung der metallischen Oberfläche eines Gegenstandes aus Stahl-Blech für die direkte Emaillierung

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US (1) US5766374A (de)
EP (1) EP0765952B1 (de)
JP (1) JPH09111474A (de)
AT (1) ATE203285T1 (de)
CA (1) CA2186327A1 (de)
DE (1) DE69613923T2 (de)
ES (1) ES2158261T3 (de)
FR (1) FR2739396B1 (de)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
EP0866147A1 (de) * 1997-03-21 1998-09-23 Sollac Herstellungsverfahren eines Gegenstandes aus Stahlblech und direkt-Emailliert

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US7514153B1 (en) 2005-03-03 2009-04-07 The United States Of America As Represented By The Secretary Of The Navy Method for deposition of steel protective coating
CN109735853A (zh) * 2019-02-15 2019-05-10 昆山正通铭金属有限公司 卷线的酸洗工艺
DE102021201881A1 (de) * 2021-02-26 2022-09-01 BSH Hausgeräte GmbH Verfahren zum herstellen eines emaillierten stahlbauteils, emailliertes stahlbauteil, sowie verwendung davon

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FR1237493A (fr) * 1958-10-20 1960-07-29 Pfizer & Co C Perfectionnements apportés aux procédés pour l'émaillage de métaux
FR2020356A1 (de) * 1968-10-10 1970-07-10 Bayer Ag
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US2569453A (en) * 1949-09-14 1951-10-02 Poor & Co Vitreous enamel base stock, vitreous enameled articles and method
FR1237493A (fr) * 1958-10-20 1960-07-29 Pfizer & Co C Perfectionnements apportés aux procédés pour l'émaillage de métaux
FR2020356A1 (de) * 1968-10-10 1970-07-10 Bayer Ag
FR2196400A1 (de) * 1972-08-07 1974-03-15 Kawasaki Steel Co

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0866147A1 (de) * 1997-03-21 1998-09-23 Sollac Herstellungsverfahren eines Gegenstandes aus Stahlblech und direkt-Emailliert

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ES2158261T3 (es) 2001-09-01
ATE203285T1 (de) 2001-08-15
EP0765952B1 (de) 2001-07-18
DE69613923T2 (de) 2001-11-22
CA2186327A1 (fr) 1997-03-29
FR2739396B1 (fr) 1997-10-24
JPH09111474A (ja) 1997-04-28
DE69613923D1 (de) 2001-08-23
US5766374A (en) 1998-06-16
FR2739396A1 (fr) 1997-04-04

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