Method of treatment of a running ferrous alloy sheet and treatment line for its implementation

Abstract

A method of treatment of a running ferrous alloy sheet containing at least one easily oxidized element is provided. The method includes a step of immersion of the sheet in a molten oxides bath. The molten oxides bath has a viscosity between 0.3.10.sup.3 Pa.Math.s and 3.10.sup.1 Pa.Math.s, the surface of the bath is contact with a non-oxidizing atmosphere, and the molten oxides are inert towards iron. The residence time of the running sheet in the bath is at least 1 s and the residues of oxides remaining on the surfaces of the sheet at the exit of the bath are eliminated. A treatment line of a ferrous alloy sheet for implementing the method, is provided. The treatment line includes a molten oxides bath having a viscosity between 0.3.10.sup.3 and 3.10.sup.1 Pa.Math.s. The surface of the bath is contact with a non-oxidizing atmosphere, and the molten oxides are inert towards iron. Mechanical devices for eliminating the residues of molten oxides remaining on the surfaces of the ferrous alloy sheet are at the exit of the molten oxides bath.

Claims

1. A method of treatment of a running ferrous alloy sheet containing at least one easily oxidized element, comprising the steps of: immersing the ferrous alloy sheet in a molten oxides bath, the molten oxides bath having a viscosity between 0.3.10.sup.3 Pa.Math.s and 3.10.sup.1 Pa.Math.s, a surface of the molten oxides bath being in contact with a non-oxidizing atmosphere, the molten oxides being inert towards iron; running the sheet in the molten oxides bath for a residence time of at least 1 s; and eliminating residues of molten oxides remaining on surfaces of the ferrous alloy sheet at an exit of the bath.

2. The method of treatment according to claim 1, wherein the running sheet is, then, immersed into a coating bath of molten metal or metal alloy.

3. The method of treatment according to claim 1, wherein the residence time of the running sheet in the molten oxides bath is between 1 and 10 s.

4. The method of treatment according to claim 1, wherein before an entry of the sheet into the molten oxides bath, the sheet undergoes a thermal treatment.

5. The method of treatment according to claim 1, wherein a composition of the molten oxides bath comprises: 45% wB.sub.2O.sub.390% w; and 10% wLi.sub.2O45% w.

6. The method of treatment according to claim 5, wherein the composition of the molten oxides bath further includes between 0.1% and 20% of at least one of: Na.sub.2O, CaO, K.sub.2O.

7. The method of treatment according to claim 1, wherein the at least one easily oxidized element is at least one element chosen among: Si, Mn, Al, Cr, B, P.

8. The method of treatment according to claim 2, wherein said coating bath is a bath of molten Zn or Zn alloy.

9. A treatment line of a running ferrous alloy sheet for implementing the method of treatment according to claim 1, comprising: a molten oxides bath having a viscosity between 0.3.10.sup.3 and 3.10.sup.1 Pa.Math.s, a surface of the bath being in contact with a non-oxidizing atmosphere, the molten oxides being inert towards iron and an elimination device for eliminating residues of molten oxides remaining on surfaces of the ferrous alloy sheet at an exit of the molten oxides bath.

10. The treatment line according to claim 9, further comprising a heating device for heating the ferrous alloy sheet located upstream of the molten oxides bath.

11. The treatment line according to claim 9, further comprising a coater for coating the ferrous alloy sheet with a molten metal or metal alloy located downstream of the molten oxides bath.

12. The treatment line according to claim 11, wherein the molten metal or metal alloy is Zn or Zn alloy.

13. The treatment line according to claim 9, wherein the elimination device includes nozzles which project a gas onto the sheet surface.

14. The treatment line according to claim 9, wherein the elimination device includes a cooling device for the sheet.

15. The treatment line according to claim 9, wherein the elimination device includes mechanical devices.

16. The treatment line according to claim 10, wherein the heating device is an oven.

17. The treatment line according to claim 11, wherein the coater is a coating bath.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The invention will be better understood thanks to the following description, which refers to the appended figures:

(2) FIG. 1, which shows an example of a treatment line including coating operations, which can be used to implement the invention;

(3) FIG. 2, which shows a Glow Discharge Optical Emission Spectrometry (GDOES) in depth profile, made before and after dipping a TWIP steel in an oxide bath at 800 C. during 1, 3, 10 or 30 seconds,

(4) FIG. 3, which shows a GDOES in depth profile made before and after dipping the same TWIP steel as the one of FIG. 2, in an oxide bath at 700 C. during 1, 3, 10 or 30 seconds.

DETAILED DESCRIPTION

(5) As illustrated in FIG. 1, a cold rolled steel sheet 1, which contains significant amounts of easily oxidizable elements as said before, continuously runs through the different modules of the line, and is moved by a group of transport rolls 2. This cold rolled sheet then crosses an oven 3 placed under a non-oxidizing or reducing atmosphere, like pure argon, pure nitrogen, or a mixture of one of these gases with hydrogen. This oven 3 may have two functions.

(6) The first function, which is the most classical since it is met on all continuous annealing ovens in galvanizing lines, is to perform an annealing of the running sheet 1, by bringing it to a temperature allowing this thermal treatment, and which can be as high as 900 C. for a carbon steel, or 1100 C. for a stainless steel, during a time period sufficient for this thermal treatment to be performed on the whole sheet thickness. Most generally, the duration of this time period is 60 s for a carbon steel and some seconds for a stainless steel. It depends mainly on the sheet temperature to be reached and on the speed of the sheet 1. If necessary, the oven 3 may by followed by a cooling device which sets the temperature of the sheet 1 at a value convenient for its entrance into the molten oxides bath 6.

(7) The second possible function of this oven 3 is merely to heat the sheet 1 at a temperature which is compatible with the following step of the treatment, as it shall be seen later on, without having in view the performing of a particular metallurgical treatment on the sheet 1.

(8) The steel sheet 1, then, crosses a surface cleaning module 4. This cleaning module 4 comprises a vessel 5 containing a bath 6 of molten oxides which are inert towards iron. In other words, these oxides do not chemically react with the metallic surfaces of the sheet 1. The molten oxides bath only dissolves the oxides present on the surface before dipping into it.

(9) In this embodiment, the bath 6 has a temperature TB equal to or higher than the temperature TS of the steel sheet 1 when it enters the bath 6, and has a viscosity at this temperature TB between 0.3.103 Pa.Math.s and 3.101 Pa.Math.s. The temperature TB of the bath 6 is set between 600 and 900 C., and preferably between 700 C. and 800 C. The bath 6 is kept at said temperature TB by heating means (not shown) such as induction heating means or heat exchangers associated with a circulating pump.

(10) Generally speaking, the temperature of the bath usually lies between 600 and 1100 C., with an upper limitation at the temperature where the molten oxides bath begins to evaporate.

(11) The composition of the bath 6 is, for example, between 45% and 90% in weight of B2O3 (boundaries included, as for all the other contents), between 10% and 45% in weight of Li2O, and, optionally, a total content between 0.1% and 20% of one or several oxides among Na2O, CaO and K2O. The composition of the bath 6 is chosen in relationship with the desired bath temperature, in order to obtain the bath viscosity compatible with the invention.

(12) B2O3 melts at a low temperature (460 C.), but its viscosity in the liquid state is very high. So, the bath viscosity is diminished by the addition of mainly Li2O, and possibly also of Na2O and/or the other previously cited oxides. Li2O is preferred because this oxide is very stable and will not be reduced by any alloying elements of the steel. Moreover, Na2O strongly increases the hygroscopic nature of the solidified oxides, which makes the material more difficult to handle.

(13) For example, a mixture Li2OB203 50/50% in weight melts at 650 C. (its composition is close to the eutectic of the mixture, which is at Li2OB2O3 47-53% in weight and 33%-67% in moles, and has a viscosity of 0.3.103 Pa.Math.s or less at temperatures of 665 C. or more. If a lower temperature is required for advantageously implementing the process of the invention (for example because a lower temperature is less energy-consuming), Na2O, CaO or K2O can be added in the amounts cited above. That makes possible to have the required viscosity for the bath 6 at a temperature between 600 and 680 C. If the bath temperature is set at a relatively high value (up to 900 C., for example), it is often sufficient to have a Na2O content of 10% or lower, according to the balance between the B2O3 and Li2O contents.

(14) The residence time of the sheet in the molten oxides bath 6 depends, of course, on the running speed of the sheet 1 and of the geometry of the vessel 5. It may be as low as 1 s, as shown by experimental studies, if the quantity of oxides to be removed from the surfaces of the sheet 1 is not too high, and if these oxides are not very adherent to the sheet 1. Higher residence times, between 1 and 10 s, may be useful for obtaining more surely a complete cleaning of the sheet 1, and can be obtained, for example, by a regulation of the dipping length inside the crucible.

(15) No upper limit for the residence time necessary for cleaning the surfaces of the sheet 1 exists. Most generally, it will not be useful to have a residence time higher than 5 s, if the cleaning of the sheet surfaces is the only function of the molten oxides bath 6. If the function of the molten oxides bath (5) is also to perform a thermal treatment on the sheet (1), the residence time may be sensibly higher, for example 30 s or 1 min.

(16) The bath 6 is placed under a non-oxidizing atmosphere for iron, composed for example of N2 and H2 gases (for example N2+1% H2). The bath 6 is preferably stirred by stirring means (not shown) such as bubbling means or any other known stirring devices.

(17) After the cleaning module 4, the steel sheet 1 runs through a wiping module 7, in which the residual molten oxides remaining on the surfaces of the steel sheet 1 are eliminated. These residual molten oxides can be easily and quickly removed from the surfaces, thanks to the non reactivity of the strip with the molten oxides and thanks to the value of specific viscosity 11 of the bath 6, and this step does not slow down the production. Said wiping module 7 can include any suitable means, such as one or several gas nozzles 8, and/or brushes, or any other means allowing the removal of the remaining molten or solidified oxides droplets of the surfaces of the steel sheet 1. If the oxides are removed by gas blowing, the gas is preferably hot (550 C. at least) for avoiding a solidification of the oxides droplets which would make them difficult to remove by gas blowing. If the oxides droplets are already solidified, a brushing performed at a high temperature (450-550 C.) is optimal.

(18) The steel sheet 1, then, runs through a coating module 9, such as a galvanization module where the steel sheet 1 is immersed into a bath 10 of molten zinc or zinc alloy, as is classically known.

(19) From its entrance into the oven 3 to its entrance into the coating bath 10, the steel sheet 1 is placed under a non-oxidizing atmosphere by means of one 14 or several snouts in which a neutral (N2) or reductive (N2H2) atmosphere is kept.

(20) If the temperature TS of the steel sheet 1 as it enters the galvanization bath 10 is too high to guarantee a good adhesion of the zinc coating, the steel sheet 1 can optionally run through a cooling module 11 placed before the coating module 9. In the example shown on FIG. 1, this cooling module 11 is set just after the wiping module 7, but it could be placed closer to the coating module 9. Placing the cooling module 11 relatively remote from the coating module 9 allows to easily placing between them a set of brushes 12, which can eliminate the last traces of solidified oxides which might remain of the surfaces of the sheet 1. This cooling module can include, for example, nozzles projecting water on the steel sheet 1, or can be any cooling module commonly used in classical hot dipping lines. The cooling module 11, if present, must set the sheet 1 at a temperature which is compatible with a good performing of the coating operation. When the sheet 1 enters the coating bath 10, its temperature must not be too high, in order not to impair the adhesion of the Zn coating, and it must not be too low in order not to excessively cool the coating bath 10. Most generally, this temperature can be set at about 10-20 C. above the coating bath temperature.

(21) After its exit from the coating bath 10, the sheet 1, as it is known in the art, is treated by a device 13 (such as a gas blowing device) which sets the thickness of the coating layer.

(22) The galvanization step is, in the described example, performed on the same treatment line than the cleaning of the sheet 1. But it would be conceivable to perform it on a separate line, provided that a reoxidation of the surfaces of the sheet 1 is carefully avoided before the galvanization (or any other type of coating operation).

(23) In the bath 6, the molten oxides get combined with the oxides which remain at the surfaces of the sheet 1, and remove them from the surfaces, according to the invention.

(24) FIG. 2 shows that the Mn oxide, which grow on the surface of a TWIP steel containing 20% Mn (gray area under the dot line), during the annealing in a radiant tube furnace containing N2+5% H2+0.04% H2O, is quite completely eliminated after a short dipping of 1 second in a reference oxide bath at 800 C. containing 50% B2O3 and 50% Li2O. Longer dipping times do not affect the surface chemistry.

(25) The TWIP steel composition used for such trial includes 23% of Mn.

(26) FIG. 3 shows that the same observation is made if the oxide bath temperature is kept at 700 C., all trial conditions being identical with the trial of FIG. 2.

(27) In a second embodiment of the invention, the oven 3 may be suppressed, and the usually performed annealing operation takes place in the molten oxides bath itself, if:

(28) the bath temperature is set at a value which allows to obtain the metallurgical transformations required by the annealing;

(29) and the residence time of the sheet 1 in the bath 6 is sufficiently high for obtaining these metallurgical transformations; from a few seconds up to, for example 30 or 60 s; these durations are often sufficient to this end, depending on the sheet composition and thickness, and of the kinetics of the desired metallurgical transformation.

(30) Also, a first thermal treatment may be performed in the oven 3, and a second treatment at a same or different temperature may be performed in the molten oxides bath 5.

(31) The invention is particularly efficient on the following classes of steels, which contain easily oxidized elements in significant amounts:

(32) interstitial-free steels, which may contain up to 0.1% by weight of Ti;

(33) dual-phase steels such as DP 500 up to DP 1500 steels which may contain about up to 3% by weight of Mn in association with up to 1% by weight of Si, Cr and/or Al;

(34) TRIP steels, like TRIP 780 steel which contains for example about 1.6% by weight of Mn and 1.5% by weight of Si;

(35) TRIP or dual-phase steels containing P;

(36) TWIP steels which have a very high content in Mn (typically 17-25% by weight),

(37) low density steels such as FeAl steels which may contain for example up to 10% by weight of Al;

(38) stainless steels, which have a very high chromium content (typically 13-25% by weight), associated with other alloying elements (Si, Mn, Al.)