EP0848076B1 - Procédé de revêtement au trempé d'une tôle d'acier; tôle zinguee ou aluminiée obtenue par ce procédé - Google Patents
Procédé de revêtement au trempé d'une tôle d'acier; tôle zinguee ou aluminiée obtenue par ce procédé Download PDFInfo
- Publication number
- EP0848076B1 EP0848076B1 EP97402985A EP97402985A EP0848076B1 EP 0848076 B1 EP0848076 B1 EP 0848076B1 EP 97402985 A EP97402985 A EP 97402985A EP 97402985 A EP97402985 A EP 97402985A EP 0848076 B1 EP0848076 B1 EP 0848076B1
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- EP
- European Patent Office
- Prior art keywords
- coating
- iron
- layer
- sheet
- metal
- 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
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 41
- 239000010959 steel Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 32
- 238000003618 dip coating Methods 0.000 title description 3
- 229910000680 Aluminized steel Inorganic materials 0.000 title 1
- 229910001335 Galvanized steel Inorganic materials 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 99
- 238000000576 coating method Methods 0.000 claims abstract description 95
- 239000011248 coating agent Substances 0.000 claims abstract description 81
- 229910052742 iron Inorganic materials 0.000 claims abstract description 47
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 29
- 239000000956 alloy Substances 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 11
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 69
- 229910052782 aluminium Inorganic materials 0.000 claims description 48
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000137 annealing Methods 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 13
- 238000005275 alloying Methods 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000002344 surface layer Substances 0.000 claims description 9
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 229910000742 Microalloyed steel Inorganic materials 0.000 claims description 2
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims 4
- 229910000851 Alloy steel Inorganic materials 0.000 claims 1
- 229910015392 FeAl3 Inorganic materials 0.000 claims 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims 1
- 229910000423 chromium oxide Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000009434 installation Methods 0.000 description 11
- 238000000151 deposition Methods 0.000 description 9
- 238000010791 quenching Methods 0.000 description 8
- 230000000171 quenching effect Effects 0.000 description 8
- 229910000676 Si alloy Inorganic materials 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910000640 Fe alloy Inorganic materials 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical group O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- 238000005269 aluminizing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000011651 chromium Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001080024 Telles Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 iron-aluminum-silicon Chemical compound 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/026—Deposition of sublayers, e.g. adhesion layers or pre-applied alloying elements or corrosion protection
Definitions
- the coating conditions in particular the recrystallization heat treatment atmosphere and the nature of the bath, are therefore best suited to the formation and wetting of a surface of pure iron.
- the disadvantage of dipping steel sheet coating processes is that the coating conditions must be adapted to the type of steel grade to to coat, in particular according to the nature and the proportion of the elements addition it contains, to obtain a wettable surface and a coating adherent.
- the addition, in the bath, of an alloying inhibitor such as aluminum, makes it possible to limit the interfacial layer (here: Fe 2 Al 5 ) to a very small thickness, generally less than 0.01 ⁇ m.
- the object of the invention is, on a dip coating line, to avoid to have to significantly modify the coating conditions according to the nuances steel to be coated.
- the object of the invention is also, in particular in the case of aluminizing, to make more resistant and / or higher-grade coatings by dipping in aluminium.
- the function of the first sublayer is essentially a function "Barrier” or “anti-ally” between the elements of the substrate, in particular the iron, and those of the metallic coating, such as generally zinc and / or aluminum; as such, the first underlay plays a role comparable to that of silicon in an aluminum bath, or that of aluminum in a zinc bath, that is to say a role of inhibition of the alliance with the substrate.
- this first underlay must therefore be sufficient high to form a barrier to the diffusion of the elements of the sheet metal substrate towards its surface, but must remain sufficiently small (less than or equal to 0.1 ⁇ m) to avoid risks of flaking of the coated sheet (for example flaking after folding).
- the function of the second sublayer is essentially a function "wetting" in the coating bath; the nature of this second underlay must therefore be adapted to that of the bath; if necessary, a second function of this second sublayer is to provide a “Resource” or controlled quantity of elements of addition and of alloying coating applied by dipping.
- this first undercoat is applied before the annealing heat treatment step, its function is also to limit diffusion towards the surface of the elements of addition of steel, where some of them may oxidize in the annealing atmosphere.
- the continuous coating installation includes, from upstream to downstream, cleaning means, means for depositing a first undercoat thin oxide, means for depositing a second thin sublayer metal, heat treatment means, quenching means, means for wringing and regulating thickness and means for solidification.
- the coating installation also includes means for making continuously scroll the sheet metal strip to be coated in the installation.
- the means for depositing a first sub-layer and the means for deposition of a second sub-layer can be for example means of vacuum deposition, electrodeposition deposition means, or means chemical vapor deposition.
- the first embodiment of the invention relates to galvanization without alloy: we will therefore use a zinc bath with aluminum additive at more than 0.15% to inhibit the iron-zinc alloy in a conventional manner.
- Zinc-based coating called non-alloy galvanizing, the average iron content remains below about 1%, while being higher than that of iron in the bath (which is generally 0.03% in weight).
- the sheet to be coated therefore runs through the coating installation using the scrolling means.
- the sheet metal surface to be coated is cleaned, for example by passing through an open flame.
- a oxide underlay of average thickness between 0.01 and 0.1 ⁇ m.
- this underlay must be high enough to form a barrier to the diffusion of the elements of addition of the steel from the sheet to its surface, but sufficiently small (less than or equal to 0.1 ⁇ m) to avoid risks of flaking of the coated sheet (for example when bending).
- this first sub-layer is adapted to provide one or more oxides as stable as possible under the conditions of the stages following of the process.
- the nature of the first sub-layer is oxide of chromium (trivalent) or zirconium oxide.
- this second sub-layer is, in the present case of non-alloy coating, adapted to provide the iron resources which will be necessary, at the time of quenching, to form a conventional inhibition layer of the Fe 2 Al 5 type. ; as this inhibition layer which forms on soaking is always very thin, a thickness of less than 0.5 ⁇ m of iron for this second sub-layer will always in practice provide a sufficient resource.
- this second sub-layer must, conversely, remain low enough to prevent the formation of iron-zinc alloy in quantity significant, which would risk dispersing in the thickness of the coating layer and deteriorate its properties.
- the surface obtained has good wettability thanks to the second underlay, external, of metallic iron.
- this preliminary surface preparation is that it can be fixed thus a “universal” surface identical for all steel grades to coating in the same installation, and that we can then use the same dip coating conditions (annealing atmosphere, temperature soaking bath etc.) for all these steel grades (for one type of coating given).
- the procedure is a conventional, known in itself: heat annealing treatment of recrystallization, quenching, spinning to regulate the thickness deposited and finally solidification of the coating.
- the first and second sublayers have been applied before the annealing heat treatment, the first undercoat prevents the diffusion towards the surface of the elements of addition of steel and their oxidation at vicinity of this surface.
- the first and second sub-layers after the annealing heat treatment step are advantageous because a deterioration of the "bi-layer is avoided "By heat treatment, the risk is all the greater as this" bi-layer Is thick, as is generally the case with alloy coatings described below.
- the "barrier" function of the first undercoat makes it possible to avoid, during tempering, the formation of "outburst” (in English) or alloy growths in the substrate-coating interface.
- the second embodiment of the invention relates to galvanization with ally; for this purpose, a zinc bath will be conventionally used aluminum additive less than 0.15% (or without aluminum); installation then comprises, downstream, conventional heat treatment means of alliance.
- the thickness of the first sub-layer (oxide) must also be high enough to form a barrier to diffusion iron from the substrate in the coating, at processing temperatures thermal alloy (conventionally around 500 ° C in the case of zinc coatings) which are generally lower than temperatures annealing (conventionally around 800 ° C).
- the structure of an alloyed galvanized coating is laminated in several superimposed sublayers of different iron-zinc alloy phases, richer in zinc from the surface, richer in iron from the substrate-coating interface.
- Alloyed galvanized coating taken as a whole generally an average iron content of between 8 and 14% by weight.
- the invention in particular to the first oxide sublayer, can now adapt in a manner known per se the conditions of the alloy heat treatment to obtain an alloyed galvanized coating whose structure is no longer stratified into several different phases of alloys iron-zinc; a coating is then obtained which no longer contains, essentially, only one alloy phase in its thickness.
- the thickness of this layer is generally greater than 6 ⁇ m.
- the structure of the coating layer is therefore homogeneous in its thickness ; the phase which mainly constitutes it may obviously contain impurities or inclusions.
- alloyed galvanized sheets according to the invention have properties different depending on the nature of this phase; depending on the case, we thus obtain a very good resistance to dusting, or very good resistance to flaking, or very good hardness, or even other known properties attached to the phase considered.
- the nature of the coating can easily be adapted galvanized alloy depending on the use of the sheet.
- the third embodiment of the invention relates to galvanization without alloying using a zinc bath with aluminum additive at less than 0.15%, that is to say a zinc bath normally used in the prior art for the coating of zinc alloy coating.
- the thickness of this second sublayer is less than 0.5 ⁇ m.
- An advantage of the invention is therefore to be able to use the same types baths for non-alloy coatings and for alloy coatings.
- the invention therefore makes it possible to facilitate the management of the metal baths of coating.
- the fourth embodiment of the invention relates to aluminization "Without alliances": a bath will therefore be used in a conventional manner of aluminum containing more than 6% of silicon to limit the alloy at the interface steel-coating.
- a non-alloyed aluminization is a coating based on aluminum with an average iron content of around 10%, while being higher than that of iron in the bath (which is generally around 3% in weight).
- the sheet metal surface to be coated is cleaned and then the treatment is carried out thermal annealing, as for a conventional aluminizing operation.
- an oxide undercoat of medium thickness is deposited between 0.01 and 0.1 ⁇ m and previously adapted to the barrier function described.
- the nature of the first sub-layer is oxide of chromium (trivalent) or zirconium oxide.
- the deposition means of the second sub-layer it is deposited then a sub-layer of a phase of an alloy of iron and aluminum which, at solid state, is likely to be in equilibrium with the coating bath to liquid state.
- the parameters that define this balance and, therefore, said phase and its composition include the bath temperature during the soaking step and the composition of the bath, which in practice is saturated with iron.
- the silicon content of the bath being greater than 6%, preferably said alloy of iron and aluminum corresponds to the so-called ⁇ 5 phase or to the so-called phase ⁇ 6 which are alloys of aluminum, iron and silicon.
- the ⁇ 5 phase has a hexagonal structure; it is sometimes called ⁇ H or H; the iron content of this phase is generally between 29 and 36% by weight; the silicon content of this phase is generally between 6 and 12% by weight; the balance consists mainly of aluminum.
- the ⁇ 6 phase has a monoclinic structure; it is sometimes called ⁇ or M; the iron content of this phase is generally between 26 and 29% in weight ; the silicon content of this phase is generally between 13 and 16% by weight; the balance consists mainly of aluminum.
- this second sub-layer is, in the present case of non-alloy coating, suitable for providing good adhesion to the layer of aluminum to be applied by dipping.
- the procedure is a classic, known in itself: soaked in the coating bath, spin to regulate the thickness deposited and finally solidification of the coating.
- a steel sheet coated with an aluminum-silicon alloy is then obtained. comparable to those of the prior art with, at the process level, the advantages identical to those previously described, in particular those of the first embodiment.
- the interfacial layer is considered fragile; this drawback results in the appearance of cracks in the coating when the sheet is bent; the addition of more than 6% of silicon in the bath is generally intended to limit the thickness of this interfacial layer to a value of the order of 3 ⁇ m.
- This surface layer contains for example of the order of 3% by weight of iron, of the order of 9% by weight of silicon, the rest being essentially made of aluminum; this layer therefore generally comprises phase inclusions based on silicon or aluminum alloy, iron and silicon; it seems that the presence of these phases leads to a weakening of this surface layer and a decrease in corrosion protection.
- the thickness of the second sub-layer according to the invention is weak, in particular less than 0.5 ⁇ m
- a coating is obtained whose interfacial layer of iron-aluminum-silicon alloy has a thickness less than that encountered in aluminized sheets at quenched from the prior art, in particular less than 1 ⁇ m.
- the total thickness of the metal layer is more than 6 ⁇ m.
- the aluminum content of the surface layer depends on the content of aluminum in the coating bath; it is generally greater than 80%; it is commonly of the order of 87% by weight.
- the average iron content of the coating (which takes into account the iron contained in the interfacial layer) is then much less than 10% in weight; it is then less than or equal to 6% by weight.
- aluminized sheets according to the invention having the structure previously described using a bath aluminum with a silicon content of less than 6%, i.e. a bath - pondered to lead to alloyed aluminum coatings.
- the coating bath contains little or no of an alloying inhibitor, such as silicon, a sheet coated with a aluminum-based layer with an interfacial alloy layer yet a small thickness.
- an alloying inhibitor such as silicon
- the two sublayers according to the invention therefore serve as an inhibitor to replace the silicon in the bath.
- the surface layer of the coating then contains much less of inclusions of the phases mentioned above, which improves the resistance to coating cracking and corrosion protection.
- the following example illustrates the first embodiment of the invention:
- the first is deposited and the second vacuum sublayers by magnetron sputtering.
- First sublayer Cr2O3 - thicknesses: a test at 30 nm and a test at 50 nm.
- Second undercoat pure iron - thicknesses: a test at 30 nm and a test at 50 nm.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating With Molten Metal (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
- Laminated Bodies (AREA)
Description
- on nettoie la surface de ladite tôle à revêtir,
- on effectue un traitement thermique de recuit, notamment de recristallisation, de ladite tôle nettoyée,
- on trempe ladite tôle traitée dans un bain liquide de métal de revêtement,
- on extrait ensuite la tôle du bain,
- et on solidifie la couche métallique de revêtement entraínée sur la tôle à la sortie dudit bain.
- on applique sur ladite surface une première sous-couche à base d'au moins un oxyde d'épaisseur moyenne comprise entre 0,01 et 0,1 µm,
- et on applique ensuite, sur ladite première sous-couche, une deuxième sous-couche métallique contenant au moins 20% en poids de fer.
- ladite première sous-couche et ladite deuxième sous-couche sont appliquées après l'étape de recuit.
- ledit acier est un acier allié ou microallié contenant des éléments d'addition oxydables dans les conditions dudit traitement thermique de recuit, notamment du silicium.
- tôle revêtue d'une couche métallique à base d'alliage de fer et de zinc appliquée au trempé caractérisée en ce que ladite couche est homogène en épaisseur et est principalement constituée d'une seule phase d'alliage fer-zinc.
- tôle revêtue d'une couche métallique à base d'aluminium appliquée au trempé, ladite couche étant stratifiée et comprenant une couche interfaciale composée essentiellement d'un ou plusieurs alliages à base de fer et aluminium, caractérisée en ce que l'épaisseur de ladite couche interfaciale est inférieure à 1 µm ; de préférence, la couche stratifiée comprend également une couche superficielle dont la teneur en aluminium est supérieure ou égale à 90%.
- on applique la première sous-couche et la deuxième sous-couche après le traitement thermique de recuit ;
- l'épaisseur de la deuxième sous-couche (de fer métallique) est, dans le cas présent de revêtement allié, adaptée pour offrir la ressource ou quantité de fer nécessaire pour l'alliation de la couche de revêtement ; l'épaisseur de cette sous-couche est alors fonction de l'épaisseur de revêtement et du taux d'alliation visés ;
- directement après essorage de la tôle, on la traite thermiquement dans des conditions adaptées de manière à obtenir l'alliation du fer contenu dans la deuxième sous-couche avec le métal du revêtement entraíné après trempé.
- une sous-couche à base d'au moins un oxyde qui est intercalée entre le substrat d'acier et ladite couche de revêtement et dont l'épaisseur moyenne est comprise entre 0,01 et 0,1 µm ;
- une couche de revêtement d'une phase d'alliage fer-zinc, telle qu'une phase Γ, δ ou ζ.
- une couche interfaciale d'alliage d'aluminium, de fer et de silicium, se présentant par exemple sous forme de phases τ5 et/ou τ6.
- une couche superficielle présentant une composition proche de celle du bain, dont l'épaisseur est généralement sensiblement supérieure à celle de la couche interfaciale.
- une sous-couche à base d'au moins un oxyde qui est intercalée entre le substrat d'acier et ladite couche de revêtement et dont l'épaisseur moyenne est comprise entre 0,01 et 0,1 µm ;
- une couche interfaciale composée essentiellement d'un ou plusieurs alliages à base de fer et aluminium, notamment sous forme de phase dite τ5 ou τ6, dont l'épaisseur est inférieure à 1 µm.
- une couche superficielle à base d'aluminium, dont l'épaisseur est en général supérieure à 5 µm.
- recuit : maintien de la tôle à revêtir à la température de environ 800°C pendant environ 1 minute sous une atmosphère d'azote contenant 5 à 10% d'hydrogène.
- bain de zinc contenant 0,16% d'aluminium, 0,03% de fer, à 455°C.
- conditions de trempé : avant trempé, la tôle d'acier est refroidie à 470°C; le temps d'immersion étant fixé à environ 3 secondes.
- épaisseur couche déposée (après essorage) : 10 µm.
Claims (17)
- Procédé de revêtement métallique d'une tôle d'acier dans lequel :on nettoie la surface de ladite tôle à revêtir,on effectue un traitement thermique de recuit de ladite tôle nettoyée,on trempe ladite tôle traitée dans un bain liquide du métal de revêtement,on extrait ensuite la tôle dudit bain,et on solidifie la couche métallique de revêtement entraínée sur la tôle à la sortie dudit bain,on applique sur ladite surface une première sous-couche à base d'au moins un oxyde d'épaisseur moyenne comprise entre 0,01 et 0,1 µm,et on applique ensuite, sur ladite première sous-couche, une deuxième sous-couche métallique contenant au moins 20% en poids de fer.
- Procédé selon la revendication 1 caractérisé en ce que ladite première sous-couche et ladite deuxième sous-couche sont appliquées après l'étape de recuit.
- Procédé selon l'une quelconque des revendications 1 ou 2 caractérisé en ce que ledit acier est un acier allié ou microallié contenant des éléments d'addition oxydables dans les conditions dudit traitement thermique de recuit, notamment du silicium.
- Procédé selon l'une quelconque des revendications 1 à 3 caractérisé en ce que ladite première sous-couche est à base d'oxyde de chrome trivalent ou d'oxyde de zirconium.
- Procédé selon l'une quelconque des revendications 1 à 4 caractérisé en ce que :ledit métal de revêtement est à base de zinc,ladite deuxième sous-couche métallique est à base de fer.
- Procédé selon l'une quelconque des revendications 1 à 4 caractérisé en ce que :ledit métal de revêtement est à base d'aluminium,ladite deuxième sous-couche métallique est à base d'un alliage de fer et d'aluminium en équilibre avec ledit bain saturé en fer.
- Procédé selon la revendication 6 caractérisé en ce que :la teneur en silicium dudit bain est inférieure à 6%,ledit alliage de fer et d'aluminium correspond au composé FeAl3.
- Procédé selon la revendication 6 caractérisé en ce que :la teneur en silicium dudit bain est supérieure à 6%,ledit alliage de fer et d'aluminium contient également du silicium et présente une composition correspondant à une phase dite τ5 ou à une phase dite τ6.
- Procédé selon l'une quelconque des revendications précédentes pour la préparation d'un revêtement dit « non allié » au fer, caractérisé en ce que l'épaisseur moyenne de ladite deuxième sous-couche appliquée est inférieure à 0,5 µm.
- Procédé selon la revendication 9 caractérisé en ce que, lorsque ledit métal de revêtement est à base de zinc, la teneur en aluminium dans ledit bain de métal est inférieure à 0,15%.
- Procédé selon la revendication 9 caractérisé en ce que, lorsque ledit métal de revêtement est à base d'aluminium, la teneur en silicium dans ledit bain de métal est inférieure à 6%.
- Procédé selon l'une quelconque des revendications 1 à 8 pour la préparation d'un revêtement dit « allié » au fer contenant une quantité de fer prédéterminée, caractérisé en ce que :l'épaisseur de ladite deuxième sous-couche est adaptée pour fournir ladite quantité de fer du revêtement,après extraction de la tôle dudit bain, on effectue un traitement thermique d'alliation dans des conditions adaptées pour allier le fer contenu dans ladite deuxième sous-couche avec ladite couche métallique de revêtement entraínée sur la tôle.
- Tôle d'acier revêtue d'une couche métallique à base d'alliage de fer et de zinc appliquée au trempé susceptible d'être obtenue par un procédé selon la revendication 12, caractérisée en ce que ladite couche est homogène en épaisseur et est principalement constituée d'une seule phase d'alliage fer-zinc.
- Tôle d'acier revêtue d'une couche métallique à base d'aluminium appliquée au trempé susceptible d'être obtenue par un procédé selon l'une quelconque des revendications 6 à 8, et 9 et 11 dépendantes de l'une quelconque des revendications 6 à 8, ladite couche étant stratifiée et comprenant une couche interfaciale composée essentiellement d'un ou plusieurs alliages à base de fer et aluminium, caractérisée en ce que l'épaisseur de ladite couche interfaciale est inférieure à 1 µm.
- Tôle selon la revendication 14 dont ladite couche métallique stratifiée comprend également une couche superficielle caractérisée en ce que en ce que la teneur en aluminium dans ladite couche superficielle est supérieure ou égale à 90%.
- Tôle selon l'une quelconque des revendications 13 à 15 caractérisée en ce qu'elle comporte une sous-couche à base d'au moins un oxyde qui est intercalée entre le substrat d'acier et ladite couche de revêtement et dont l'épaisseur moyenne est comprise entre 0,01 et 0,1 µm.
- Tôle selon l'une quelconque des revendications 13 à 16 caractérisée en ce que l'épaisseur de ladite couche métallique est supérieure à 6 µm.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9615195 | 1996-12-11 | ||
FR9615195A FR2756846B1 (fr) | 1996-12-11 | 1996-12-11 | Procede de revetement au trempe d'une tole d'acier |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0848076A1 EP0848076A1 (fr) | 1998-06-17 |
EP0848076B1 true EP0848076B1 (fr) | 2001-08-22 |
Family
ID=9498536
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97402985A Expired - Lifetime EP0848076B1 (fr) | 1996-12-11 | 1997-12-10 | Procédé de revêtement au trempé d'une tôle d'acier; tôle zinguee ou aluminiée obtenue par ce procédé |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0848076B1 (fr) |
AT (1) | ATE204614T1 (fr) |
DE (1) | DE69706269T2 (fr) |
DK (1) | DK0848076T3 (fr) |
ES (1) | ES2162220T3 (fr) |
FR (1) | FR2756846B1 (fr) |
PT (1) | PT848076E (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2312011A1 (fr) | 2009-10-15 | 2011-04-20 | Georg Fischer Automotive AG | Procédé de revêtement métallique d'une pièce de formage coulée et pièce de formage coulée fabriquée selon ce procédé |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
LU60512A1 (fr) * | 1970-03-11 | 1971-11-08 | ||
DE3150998C2 (de) * | 1981-12-23 | 1984-06-20 | Peri-Werk Artur Schwörer GmbH & Co KG, 7912 Weißenhorn | Verfahren zum Feuerverzinken und zum Feuerverzinken bestimmtes Teil |
JPS61194186A (ja) * | 1985-02-25 | 1986-08-28 | Nippon Steel Corp | 複合鋼管の製造方法 |
JPS61243162A (ja) * | 1985-04-19 | 1986-10-29 | Nippon Steel Corp | 耐熱性に優れたAl系溶融メツキ鋼板の製造法 |
JP2769350B2 (ja) * | 1989-03-28 | 1998-06-25 | 新日本製鐵株式会社 | 溶融めっき鋼板の製造方法 |
JPH05132747A (ja) * | 1991-11-12 | 1993-05-28 | Kawasaki Steel Corp | 溶融Znめつきクロム含有鋼板の製造方法 |
-
1996
- 1996-12-11 FR FR9615195A patent/FR2756846B1/fr not_active Expired - Fee Related
-
1997
- 1997-12-10 EP EP97402985A patent/EP0848076B1/fr not_active Expired - Lifetime
- 1997-12-10 ES ES97402985T patent/ES2162220T3/es not_active Expired - Lifetime
- 1997-12-10 PT PT97402985T patent/PT848076E/pt unknown
- 1997-12-10 AT AT97402985T patent/ATE204614T1/de active
- 1997-12-10 DE DE69706269T patent/DE69706269T2/de not_active Expired - Lifetime
- 1997-12-10 DK DK97402985T patent/DK0848076T3/da active
Also Published As
Publication number | Publication date |
---|---|
FR2756846A1 (fr) | 1998-06-12 |
DE69706269D1 (de) | 2001-09-27 |
DK0848076T3 (da) | 2001-11-12 |
ES2162220T3 (es) | 2001-12-16 |
PT848076E (pt) | 2002-01-30 |
DE69706269T2 (de) | 2002-05-08 |
ATE204614T1 (de) | 2001-09-15 |
FR2756846B1 (fr) | 1999-01-08 |
EP0848076A1 (fr) | 1998-06-17 |
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