METHOD OF PRODUCING A NITRIDED PACKAGING STEEL

Abstract

A nitrided packaging steel in the form of a flat steel product and method for producing a nitrided packaging steel with a carbon content of 10-1000 ppm and uncombined nitrogen, dissolved in the steel, of more than 100 ppm. The nitriding is performed in two stages: a first stage, in which a molten steel is nitrided to a nitrogen content of at most 160 ppm by introducing a nitrogen-containing gas and/or a nitrogen-containing solid into the molten steel, and a second stage, in which a flat steel product produced from the nitrided molten steel by cold rolling is treated with a nitrogen-containing gas in order to increase further the amount of uncombined nitrogen in the flat steel product. The second stage is performed in an annealing furnace, in which the flat steel product is at the same time annealed in a recrystallizing manner. The packaging steels produced are distinguished by great strength, in excess of 600 MPa, and good elongation to fracture, regularly in excess of 5%, as well as by good forming properties.

Claims

1. A method of producing a nitrided packaging steel with a carbon content of 10 to 1000 ppm and a quantity of uncombined nitrogen dissolved in the steel of more than 100 ppm, the method comprising: a) nitriding a molten steel to a nitrogen content of a maximum of 160 ppm by feeding a nitrogen-containing gas and/or a nitrogen-containing solid into the molten steel; b) casting a slab from the molten steel and hot rolling the slab to form a hot strip; c) cold rolling the hot strip to form a flat steel product; d) recrystallization annealing the cold-rolled flat steel product in an annealing furnace, in particular a continuous annealing furnace, wherein a nitrogen-containing gas is introduced into the annealing furnace and directed onto the flat steel product so as to further increase the quantity of uncombined nitrogen in the flat steel product.

2. The method as in claim 1, wherein in Step a), nitriding of the molten steel takes place by feeding nitrogen gas (N.sub.2) and/or calcium cyanamide (CaCN.sub.2) and/or manganese nitride (MnN) into the molten steel.

3. The method as in claim 1 wherein in Step d), ammonia gas (NH.sub.3) is fed into the annealing furnace.

4. The method as in claim 3, wherein the ammonia gas (NH.sub.3) in the annealing furnace is directed onto the flat steel product by means of one or a plurality of spray nozzles.

5. The method as in claim 3, wherein as a result of feeding in the ammonia gas (NH.sub.3), an ammonia equilibrium with a concentration in the range of 0.05 to 1.5% is established in the annealing furnace.

6. The method as in claim 3, wherein the ammonia equilibrium concentration resulting in the annealing furnace as a result of feeding in ammonia gas (NH.sub.3) is measured by means of an ammonia sensor.

7. The method as in claim 6, wherein the value of the ammonia equilibrium concentration measured is used to control the quantity of ammonia gas fed per unit of time into the annealing furnace.

8. The method as in claim 3, wherein in addition to ammonia gas (NH.sub.3), an inert gas, in particular nitrogen gas (N.sub.2) and/or hydrogen gas (H.sub.2), preferably a mixture of 95 wt % of nitrogen gas (N.sub.2) and 5 wt % of hydrogen gas (H.sub.2), is also fed into the annealing furnace.

9. The method as in claim 1, wherein after nitriding the cold-rolled flat steel product in the annealing furnace, the quantity of uncombined nitrogen is in a range of 100 to 500 ppm, preferably more than 150 ppm, and most preferably in a range of 200 to 350 ppm.

10. The method as in claim 1, wherein the recrystallization annealing of the cold-rolled flat steel product in Step d) is accomplished by passing the flat steel product through continuous annealing furnace in which the flat steel product is heated to temperatures of more than 600° C. and preferably to a temperature in a range of 620° C. to 660° C.

11. The method as in claim 1, wherein the carbon content of the steel is in a range of 100 to 1000 ppm and preferably in a range of 500 to 900 ppm.

12. A nitrided packaging steel in the form of a flat steel product having a thickness of less than 0.5 mm and preferably of less than 0.4 mm, especially produced by the method as in claim 1, with the packaging steel having a carbon content in a range of 10 to 1000 ppm and an average quantity of uncombined nitrogen dissolved in the steel of more than 100 ppm, wherein the concentration distribution of the uncombined nitrogen varies from the mean quantity of nitrogen by less than ±10 ppm throughout the thickness of the flat steel product.

13. The nitrided packaging steel as in claim 12, wherein the concentration distribution of the uncombined nitrogen varies from the mean quantity of nitrogen by less than ±5 ppm throughout the thickness of flat steel products.

14. The nitrided packaging steel as in claim 12, wherein the ultimate tensile strength of the packaging steel is greater than 600 MPa.

15. The nitrided packaging steel as in claim 12, wherein the mean quantity of uncombined nitrogen is greater than 150 ppm and preferably in a range of 200 and 350 ppm.

Description

[0020] This and other advantages of the packaging steel produced according to the present invention follow from the embodiment example described in greater detail below with reference to the accompanying drawings. The drawings show:

[0021] FIG. 1: a schematic representation of an annealing furnace in which the second stage of the method according to the present invention is carried out.

[0022] In an embodiment example of the method according to the present invention, first a nitrided molten steel is produced in a converter and/or in a subsequent ladle treatment [station], said molten steel having a content of free, uncombined (i.e., dissolved in the steel) nitrogen of up to 160 ppm. The alloy composition of the steel preferably meets the limit values specified by the standards for packaging steel (such as defined, e.g., in ASTM Standard A623-11 “Standard Specification for Tin Mill Products” or in “European Standard EN 10202”), with the exception of the upper limit value for the nitrogen content (which in Standard EN 10202 is given as N.sub.max=80 ppm and in AST [sic] Standard ASTM 623 as N.sub.max=200 ppm) which, because of the nitriding process, can be exceeded in the method according to the present invention. The carbon fraction is preferably in a range of 10 to 1000 ppm and most preferably in a range of 100 to 900 ppm and, as a rule, in a range of 400 to 900 ppm.

[0023] To produce the molten steel, the converter is filled with scrap and pig iron, and a blast of oxygen gas and nitrogen gas is supplied to the molten steel, said oxygen gas (O.sub.2) being blown from the top and the nitrogen gas (N.sub.2) being blown through tuyeres from the bottom into the converter. As a result, the nitrogen content that obtains in the molten steel is 70 to 120 ppm, which leads to saturation. During the production of the molten steel, the composition and, in particular, the nitrogen content of the molten steel is measured. If the chemical composition is not within the required limits (e.g., if the fraction of phosphorus is too high), oxygen gas is blown in through an oxygen lance and argon gas (Ar) through the bottom tuyeres. Since only a very small amount of carbon (C) is still contained in the steel, no excess pressure builds up and the nitrogen of is drawn in, which can lead to additional nitriding.

[0024] If the amount of (dissolved) nitrogen desired in the molten steel (which, as a rule, is approximately 120 ppm) has not yet been reached by blowing in the nitrogen gas, lime nitrogen (calcium cyanamide, CaCN.sub.2) can additionally be fed into the stream of steel exiting the converter while the converter is being emptied (tapped). The calcium cyanamide can be added for example, in the form of granules (5-20 mm).

[0025] Subsequently, the ladle is transferred to the first argon rinsing station where rinsing with argon takes place for approximately 3 minutes, using a refractory lance that is immersed in the molten steel. Following a control analysis, if necessary, rinsing in a second argon rinsing station takes place a second time for approximately 3 minutes. The ladle then goes to a third argon rinsing station. This is the last stage prior to casting. If the nitrogen content is not within the preset target range, manganese nitride (MnN), for example, in the form of a wire of MnN [sic] in a steel sheath, can be added. The amount of possibly lacking nitrogen is converted into a required amount of MnN (for example, into a required length of the MnN wire) which is added to the molten steel. The MnN is added until the preset target content of nitrogen or an upper Mn limit of the steel is obtained.

[0026] Finally, the molten steel is emptied into a tundish in order to cast a slab from the molten steel. Because of leaks and the diffusion of atmospheric nitrogen into the molten steel, the nitrogen content can increase by approximately 10 ppm. An upper limit of the amount of dissolved nitrogen in the cast steel slab of approximately 160 ppm should not be exceeded since at a nitrogen content higher than the upper limit mentioned, it is possible for defects, such as cracks or pores, to form on the slab, which lead to an undesirable oxidation.

[0027] The slab cast from the molten steel is subsequently hot-rolled and cooled to room temperature. The hot strip produced has thicknesses in a range of 1 to 4 mm and, if desired, is wound into a coil. To produce a packaging steel in the form of a flat steel product in the usual thin and ultra-thin sheet metal thicknesses, the hot strip must be cold-rolled, during the course of which the thickness is reduced by 50% up to more than 90%. Thin sheet metal is defined as sheet metal having a thickness of less than 3 mm, and an ultra-thin sheet metal has a thickness of less than 0.5 mm. Cold-rolling is accomplished by unwinding the potentially coiled hot strip from the coil, by pickling it and by feeding it into a cold rolling mill, for example, a cold rolling line.

[0028] To restore the crystal structure of the steel which had been destroyed during cold rolling, the cold-rolled steel strip must be subjected to recrystallization annealing. This is accomplished by passing the cold-rolled steel strip through a continuous annealing furnace in which the steel strip is heated to temperatures above the recrystallization point of the steel and, in particular, to temperatures above 600° C. During the course of the method carried out according to the present invention, the steel strip is further nitrided in a second stage while being subjected to recrystallization annealing. This stage is carried out in the annealing furnace by feeding a nitrogen-containing gas, preferably ammonia (NH.sub.3), into the annealing furnace.

[0029] FIG. 1 is a diagrammatic representation of a continuous annealing furnace in which the recrystallization and nitriding during the second stage take place. This furnace is configured to have a number of different zones which, in the throughput direction (strip conveyance direction V, in FIG. 1 from right to left) of the steel strip passing though the continuous annealing furnace, are disposed one behind another. In a heating zone 1 disposed on the input side of the continuous annealing furnace, the steel strip S is heated to temperatures in the range of 600° C. to 750° C. The temperature especially favorable for the second nitriding stage was found to be in a range of 620° C. to 700° C., and the temperature especially preferred was found to be in a range of 620° C. to 660° C. The best results were obtained at temperatures of approximately 640° C. These temperatures are above the recrystallization temperature of the steel, which is the reason that the steel strip S is subjected to recrystallization annealing in heating zone 1.

[0030] The heating zone 1 is adjoined by a temperature holding zone 2 in which the temperature of the steel strip S is maintained within the temperature range specified above. In the temperature holding zone 2, a plurality of cascades 3a, 3b, 3c of spray nozzles are disposed one behind another in the strip conveyance direction. Each cascade 3a, 3b, 3c comprises a plurality of nozzles 3, which, in the strip conveying direction, are disposed at a distance from and at right angles relative to one another. The nozzles 3 are connected to a gas feeding line, via which they receive a nitrogen-containing gas. The gas especially favorable for the second nitriding stage was found to be ammonia gas. By means of the nozzles 3 of the cascades, this gas is applied to the surfaces of the steel strip S passing through the furnace where it penetrates into the area near the surface of the steel strip and uniformly diffuses into the depth of the steel strip. Thus, the nitrogen is uniformly and homogeneously distributed throughout the thickness of the steel strip, and its concentration distribution for steel sheets having a thickness of less than 0.4 mm varies from the mean value by at most ±10 ppm and, as a rule, by only ±5 ppm throughout the sheet thickness.

[0031] The configuration of the preferably used nozzles 3 of the cascades is described in the German Patent Application DE 102014106135 of Apr. 30, 2014, with the content disclosed therein hereby being incorporated into the subject matter of the present application. In the application referred to, a nozzle assembly for the treatment of a flat steel product is described, said nozzle assembly comprising an outer tube and an inner tube disposed therein having a primary opening for feeding a gas flowing through the nozzle assembly into the outer tube and said outer tube having a secondary opening through which the gas can exit. The primary opening of the inner tube and the secondary opening of the outer tube are disposed so as to be offset relative to each other. Because of this arrangement, a highly homogeneous gas flow onto the surface of the flat steel product is made possible. Using this type of nozzle assembly in the method according to the present invention, the surface of the steel strip can be homogeneously exposed to the nitrogen-containing gas (ammonia) in the temperature holding zone 2 of the continuous annealing furnace, which makes it possible for nitrogen to be homogeneously diffused throughout the surface of the steel strip, in particular throughout its width, and thus for a homogeneous nitrogen-enriched and hardened surface layer to be formed.

[0032] The method of direct exposure of the steel strip (exposure to gas) to a nitrogen-containing gas by means of nozzles has two major advantages. First, only a low nitrogen concentration (NH.sub.3 concentration) in the inert gas is needed, which leads to a low consumption of nitrogen-containing gas (for example, NH.sub.3 consumption). Secondly, because of the very short exposure time, the formation of a nitride layer is avoided. Following the exposure to a nitrogen-containing gas (for example, NH.sub.3 treatment), the steel strip continues to be further annealed (preferably for more than 5 seconds) at unchanged temperatures before it is cooled. This leads to a homogenous nitrogen distribution throughout the cross section of the steel strip and thus to improved forming properties. More particularly, it makes it possible to avoid a reduction in the elongation to fracture due to lacquer aging (see page 6, lines 12-15).

[0033] To also ensure the most homogeneous formation of a nitrogen-enriched surface coating throughout the length of the steel strip S, a nitrogen-rich atmosphere with the most consistent possible nitrogen equilibrium concentration must be maintained while the steel strip S passes through the temperature holding zone 2 of the continuous annealing furnace. To ensure that this is the case, the nitrogen concentration is measured in the region of the cascades 3a, 3b, 3c comprising the nozzles 3. If ammonia is used as the nitrogen-containing gas, the ammonia concentration formed in the temperature holding zone 2 as a result of the exposure to ammonia is measured. To this end, a concentration sensor disposed outside the continuous annealing furnace is provided, which sensor may, for example, be a laser spectroscopy sensor. To measure the ammonia concentration and, therefrom, the nitrogen concentration of the gas atmosphere in the temperature holding zone 2, a gas sample drawn from the temperature holding zone 2 is transferred to said sensor. The gas sample is drawn, for example, at the point designated by the reference character 4 in FIG. 1. The concentration of nitrogen in the gas atmosphere of the temperature holding zone 2 measured by the concentration sensor is fed to a control unit which uses it to hold the amount of the nitrogen-containing gas (ammonia) sprayed through the nozzles 3 into the temperature holding zone 2 constant at a preset target value.

[0034] When ammonia is used as the nitrogen-containing gas, target values for the equilibrium concentration of ammonia in a range of 0.05 to 1.5%, and preferably lower than 1%, especially lower than 0.2%, have been proven to be especially useful. Preferably, the equilibrium concentration of ammonia is in a range of 0.1% to 1.0% and most preferably in a range of 0.1% to 0.2%.

[0035] To avoid oxidation processes on the surface of the steel strip S, it is recommended that in the temperature holding zone 2, an inert gas, in addition to the nitrogen-containing gas (ammonia), be also fed into the annealing furnace. This gas may be, for example, nitrogen gas or/or [sic; and/or] hydrogen gas. Preferably, a mixture of approximately 95% of nitrogen gas and approximately 5% of hydrogen gas is used.

[0036] In the strip conveying direction V, the temperature holding zone 2 is adjoined by a plurality of cooling zones 5, 6, wherein a more rapid cooling of the steel strip S takes place in a first cooling zone 5 and a slower cooling in a downstream second cooling zone 6.

[0037] After having undergone cooling in the cooling zones 5 and 6, the steel strip S exits the continuous annealing furnace and is dry skin pass rolled (temper rolled) to ensure that the strip has the forming properties required for the production of packaging materials. The skin pass degree varies between 0.4% and 2% depending on the intended use of the packaging steel. If necessary, the steel strip can also be wet skin pass rolled in order to further reduce the thickness by up to 43% (double reduced steel strip, “double reduced,” DR). Subsequently, the steel strip S, if desired, is transferred to a coating station in which the surface of the steel strip is, for example, electrolytically coated with a tin coating or a chromium/chromium dioxide coating (ECCS) or a lacquer coating in order to increase the corrosion resistance. It has been found that compared to the prior-art flat steel products, the packaging steels produced by means of the method according to the present invention also have improved anticorrosive properties.

[0038] Using the method according to the present invention, it is possible to produce nitrided steel strips which are distinguished by an extremely high strength of more than 600 MPa, while at the same time having an excellent elongation to fracture higher than 5% and good forming properties. The increased strength resulting from the two-stage nitriding process and the elongation to fracture are very homogeneously distributed throughout the cross section of the cold-rolled steel strip, both in and at right angles relative to the rolling direction. The reason for this is that uncombined nitrogen has been very homogeneously introduced into the steel, especially in the second nitriding stage. In addition, chemical composition analyses performed on flat steel products produced according to the present invention have also shown that at least in ultra-fine steel sheets, the nitrogen concentration introduced by nitriding varies from the mean concentration only within a narrow range of at most ±10 ppm and, as a rule, only by ±5 ppm.

[0039] Recrystallization annealing and the second nitriding stage can also be carried out in a bell-type annealing furnace instead of in a continuous annealing furnace. When using this furnace, the cold-rolled coiled steel strip S is fed into a bell-type annealing furnace where it is annealed under an inert gas atmosphere at the annealing temperatures required for recrystallization annealing of more than 520° C. In order to be able to carry out the second nitriding stage simultaneously with recrystallization annealing in the bell-type annealing furnace, bell-type annealing employs the “open coil” method. In this method, spacers are placed between the layers of a coiled steel strip in order to keep the surface of the steel strip accessible for diffusing nitrogen into it.

[0040] In the tables below, embodiment examples of flat steel products produced according to the present invention are listed in a number of variants (each referred to as “Variant”) and for different applications for the production of packaging materials and/or parts thereof (pull-tab lid for a tin can and deep-drawn twist-off caps) and compared with flat steel products produced in the prior art (without two-stage nitriding, each referred to as “Standard”) with an identical or similar steel composition (alloy components).

TABLE-US-00001 TABLE 1 Embodiment example of a packaging steel for use in the production of full-top pull-tab lids (Standard grade with C = 600-900 ppm, N = 80-140 ppm) Variant 1 Standard Two-stage Single-stage nitriding nitriding of acc. to the the molten present steel invention Chemical C [ppm] 740 750 analysis N [ppm] 122 187 Mn [ppm] 3100 3100 Al [ppm] 150 150 Si [ppm] 90 110 Cr [ppm] 290 270 Ni [ppm] 130 120 Cu [ppm] 130 70 P [ppm] 140 150 S [ppm] 50 40 Hot strip Thickness [mm] 2.0 2.0 T.sub.finish rolling [° C.] 861 854 T.sub.coiling [° C.] 571 570 Cold Strip T.sub.annealing [° C.] 670 640 Skin pass [%] 8 11 degree Final thickness [mm] 0.160 0.160 Performance Upper yield [MPa] 560 640 characteristics stress (R.sub.eh) (200° C., 20 min) Ultimate tensile [MPa] 540 644 strength (200° C., 20 min) Ear height [mm] — — (β = 1.8. Cup = 33 mm) Elongation to [%] 4.2 8.5 fracture

TABLE-US-00002 TABLE 2 Embodiment example a packaging steel for use in the production of deep-drawn twist-off caps (Standard grade with C = 10-40 ppm, N < 40 ppm) Variant 1 Variant 2 Variant 3 Two-stage Two-stage Two-stage nitriding nitriding nitriding acc. to the acc. to the acc. to the resent resent resent Standard 1 Standard 2 invention invention invention Chemical C [ppm] 23 25 28 20 17 analysis N [ppm] 15 30 110 170 180 Mn [ppm] 2100 2100 2200 2300 2300 Al [ppm] 20 20 20 180 10 Si [ppm] 220 200 190 100 230 Cr [ppm] 250 210 200 180 210 Ni [ppm] 130 110 110 150 120 Cu [ppm] 80 60 70 60 70 P [ppm] 100 90 80 90 70 S [ppm] 70 70 60 70 80 Hot strip Thickness [mm] 2.5 2.5 2.5 2.5 2.5 T.sub.finish rolling [° C.] 870 877 880 871 862 T.sub.Coiling [° C.] 631 621 620 601 618 Cold strip T.sub.annealing [° C.] 690 690 690 690 690 Skin pass degree [%] 40 40 40 40 32 Final thickness [mm] 0.140 0.154 0.140 0.140 0.140 Performance Upper yield stress [MPa] 633 598 680 685 690 characteristics (R.sub.eh) (200° C., 20 min) Ultimate tensile [MPa] 633 599 680 685 690 strength (200° C., 20 min) Ear height [mm] 0.70 0.75 0.65 0.71 0.68 (β = 1.8. Cup = 33 mm) Elongation to [%] 0.35 1.59 1.01 0.85 1.89 fracture