Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
  • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D6/00—Heat treatment of ferrous alloys
  • C21D6/002—Heat treatment of ferrous alloys containing Cr
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
  • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
  • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
  • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
  • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
  • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
  • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
  • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
  • C21D8/0226—Hot rolling
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
  • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
  • C21D8/0236—Cold rolling
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
  • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
  • C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
  • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
  • C21D8/0273—Final recrystallisation annealing

Definitions

• ferritic stainless steel with oxidation resistance, high temperature strength, and good formability characteristics. Columbium and copper are added in amounts to provide high temperature strength, and silicon and manganese are added in amounts to provide oxidation resistance.
• the present ferritic stainless steel provides better oxidation resistance than known stainless steels such as 18Cr-2Mo and 15Cr—Cb—Ti—Si—Mn. In addition, the present ferritic stainless steel is less expensive to manufacture than other stainless steels such as 18Cr-2Mo.
• the present ferritic stainless steel are produced with titanium additions and low aluminum concentration to provide room temperature formability from equiaxed as-cast grain structures, as disclosed in U.S. Pat. Nos. 6,855,213 and 5,868,875, the complete disclosures of which are each incorporated by reference herein.
• Columbium and copper are added to the ferritic stainless steel for high temperature strength and silicon and manganese are added to improve oxidation resistance.
• the ferritic stainless steel is produced using process conditions known in the art for use in manufacturing ferritic stainless steels, such as the processes described in U.S. Pat. Nos. 6,855,213 and 5,868,875. Columbium and copper are added to the ferritic stainless steel for high temperature strength and silicon and manganese are added to improve oxidation resistance. It can be produced from material having an as-cast structure of fine equiaxed grains.
• a ferrous melt for the ferritic stainless steel is provided in a melting furnace such as an electric arc furnace.
• This ferrous melt may be formed in the melting furnace from solid iron bearing scrap, carbon steel scrap, stainless steel scrap, solid iron containing materials including iron oxides, iron carbide, direct reduced iron, hot briquetted iron, or the melt may be produced upstream of the melting furnace in a blast furnace or any other iron smelting unit capable of providing a ferrous melt.
• the ferrous melt then will be refined in the melting furnace or transferred to a refining vessel such as an argon-oxygen-decarburization vessel or a vacuum-oxygen-decarburization vessel, followed by a trim station such as a ladle metallurgy furnace or a wire feed station.
• the steel is cast from a melt containing sufficient titanium and nitrogen but a controlled amount of aluminum for forming small titanium oxide inclusions to provide the necessary nuclei for forming the as-cast equiaxed grain structure so that an annealed sheet produced from this steel also has enhanced ridging characteristics.
• titanium is added to the melt for deoxidation prior to casting.
• Deoxidation of the melt with titanium forms small titanium oxide inclusions that provide the nuclei that result in an as-cast equiaxed fine grain structure.
• aluminum may not be added to this refined melt as a deoxidant.
• titanium and nitrogen can be present in the melt prior to casting so that the ratio of the product of titanium and nitrogen divided by residual aluminum is at least about 0.14.
• the steel is to be stabilized, sufficient amount of the titanium beyond that required for deoxidation can be added for combining with carbon and nitrogen in the melt but preferably less than that required for saturation with nitrogen, i.e., in a sub-equilibrium amount, thereby avoiding or at least minimizing precipitation of large titanium nitride inclusions before solidification.
• the maximum amount of titanium for “sub-equilibrium” is generally illustrated in FIG. 4 of U.S. Pat. No. 4,964,926, the disclosure of which is incorporated herein by reference.
• one or more stabilizing elements such as columbium, zirconium, tantalum and vanadium can be added to the melt as well.
• the cast steel is hot processed into a sheet.
• sheet is meant to include continuous strip or cut lengths formed from continuous strip and the term “hot processed” means the as-cast steel will be reheated, if necessary, and then reduced to a predetermined thickness such as by hot rolling. If hot rolled, a steel slab is reheated to 2000° to 2350° F. (1093°-1288° C.), hot rolled using a finishing temperature of 1500-1800° F. (816-982° C.) and coiled at a temperature of 1000-1400° F. (538-760° C.).
• the hot rolled sheet is also known as the “hot band.”
• the hot band may be annealed at a peak metal temperature of 1700-2100° F. (926-1149° C.).
• the hot band may be descaled and cold reduced at least 40% to a desired final sheet thickness.
• the hot band may be descaled and cold reduced at least 50% to a desired final sheet thickness. Thereafter, the cold reduced sheet can be final annealed at a peak metal temperature of 1800-2100° F. (982-1149° C.).
• the ferritic stainless steel can be produced from a hot processed sheet made by a number of methods.
• the sheet can be produced from slabs formed from ingots or continuous cast slabs of 50-200 mm thickness which are reheated to 2000° to 2350° F. (1093°-1288° C.) followed by hot rolling to provide a starting hot processed sheet of 1-7 mm thickness or the sheet can be hot processed from strip continuously cast into thicknesses of 2-26 mm.
• the present process is applicable to sheet produced by methods wherein continuous cast slabs or slabs produced from ingots are fed directly to a hot rolling mill with or without significant reheating, or ingots hot reduced into slabs of sufficient temperature to be hot rolled in to sheet with or without further reheating.
• Titanium is used for deoxidation of the ferritic stainless steel melt prior to casting.
• the amount of titanium in the melt can be 0.30% or less. Unless otherwise expressly stated, all concentrations stated as “%” are percent by weight.
• titanium can be present in a sub-equilibrium amount.
• the term “sub-equilibrium” means the amount of titanium is controlled so that the solubility product of the titanium compounds formed are below the saturation level at the steel liquidus temperature thereby avoiding excessive titanium nitride precipitation in the melt.
• Excessive nitrogen is not a problem for those manufacturers that refine ferritic stainless steel melts in an argon oxygen decarburization vessel. Nitrogen substantially below 0.010% can be obtained when refining the stainless steel in an argon oxygen decarburization vessel thereby allowing increased amount of titanium to be tolerated and still be at sub-equilibrium.
• sufficient time after adding the titanium to the melt should elapse to allow the titanium oxide inclusions to form before casting the melt. If the melt is cast immediately after adding titanium, the as-cast structure of the casting can include larger columnar grains. The amount of time that should elapse can be determined by one of ordinary skill in the art without undue experimentation. Ingots cast in the laboratory less than 5 minutes after adding the titanium to the melt had large as-cast columnar grains even when the product of titanium and nitrogen divided by residual aluminum was at least 0.14.
• Sufficient nitrogen should be present in the steel prior to casting so that the ratio of the product of titanium and nitrogen divided by aluminum is at least about 0.14. In some embodiments, the amount of nitrogen present in the melt is ⁇ 0.020%.
• nitrogen concentrations after melting in an electric arc furnace may be as high as 0.05%
• the amount of dissolved N can be reduced during argon gas refining in an argon oxygen decarburization vessel to less than 0.02%. Precipitation of excessive TiN can be avoided by reducing the sub-equilibrium amount of Ti to be added to the melt for any given nitrogen content.
• the amount of nitrogen in the melt can be reduced in an argon oxygen decarburization vessel for an anticipated amount of Ti contained in the melt.
• Total residual aluminum can be controlled or minimized relative to the amounts of titanium and nitrogen.
• Minimum amounts of titanium and nitrogen must be present in the melt relative to the aluminum.
• the ratio of the product of titanium and nitrogen divided by residual aluminum can be at least about 0.14 in some embodiments, and at least 0.23 in other embodiments.
• the amount of aluminum is ⁇ 0.020% in some embodiments. In other embodiments, the amount of aluminum is ⁇ 0.013% and in other embodiments, it is reduced to ⁇ 0.010%. If aluminum is not purposefully alloyed with the melt during refining or casting such as for deoxidation immediately prior to casting, total aluminum can be controlled or reduced to less than 0.020%.
• Titanium alloys may contain as much as 20% Al which may contribute total Al to the melt.
• stabilizing elements may also include columbium, zirconium, tantalum, vanadium or mixtures thereof.
• this second stabilizing element may be limited to ⁇ 0.50% when deep formability is required.
• Some embodiments include columbium in concentrations of 0.05% or less.
• Some embodiments include columbium in concentrations of 0.28-0.43%.
• Vanadium can be present in amounts less than 0.5%.
• Some embodiments of the ferritic stainless steels include 0.008-0.098% vanadium.
• the ferritic stainless steels contain 1.0-2.0% copper. Some embodiments include 1.16-1.31% copper.
• Silicon is generally present in the ferritic stainless steels in an amount of 1.0-1.7%. In some embodiments, silicon is present in an amount of 1.27-1.35%. A small amount of silicon generally is present in a ferritic stainless steel to promote formation of the ferrite phase. Silicon also enhances high temperature oxidation resistance and provides high temperature strength. In most embodiments, silicon does not exceed about 1.7% because the steel can become too hard and the elongation can be adversely affected.
• Manganese is present in the ferritic stainless steel in an amount of 0.4-1.5%. In some embodiments, manganese is present in an amount of 0.98-1.00%. Manganese improves oxidation resistance and spalling resistance at high temperatures. Accordingly, some embodiments include manganese in amounts of at least 0.4%. However, manganese is an austenite former and affects the stabilization of the ferrite phase. If the amount of manganese exceeds about 1.5%, the stabilization and formability of the steel can be affected.
• Carbon is present in the ferritic stainless steel in an amount of up to 0.02%. In some embodiments, the carbon content is ⁇ 0.02%. In still other embodiments, it is 0.0010-0.01%.
• Chromium is present some embodiments of the ferritic stainless steels in an amount of 15-20%. If chromium is greater than about 25%, the formability of the steel can be reduced.
• oxygen is present in the steel in an amount ⁇ 100 ppm.
• oxygen in the melt can be within the range of 10-60 ppm thereby providing a very clean steel having small titanium oxide inclusions that aid in forming the nucleation sites responsible for the fine as-cast equiaxed grain structure.
• Sulfur is present in the ferritic stainless steel in an amount of ⁇ 0.01%.
• Phosphorus can deteriorate formability in hot rolling and can cause pitting. It is present in the ferritic stainless steel in an amount of ⁇ 0.05%.
• nickel is an austenite former and affects the stabilization of the ferrite phase. Accordingly, in some embodiments, nickel is limited to ⁇ 1.0%. In some embodiments, nickel is present in amounts of 0.13-0.19%.
• Molybdenum also improves corrosion resistance. Some embodiments include 3.0% or less molybdenum. Some embodiments include 0.03-0.049% molybdenum.
• boron in the steels of the present invention in an amount of ⁇ 0.010%. In some embodiments, boron is present in an amount of 0.0001-0.002%. Boron can improve the resistance to secondary work embrittlement of steel so that the steel sheet will be less likely to split during deep drawing applications and multi-step forming applications.
• the ferritic stainless steels may also include other elements known in the art of steelmaking that can be made either as deliberate additions or present as residual elements, i.e., impurities from steelmaking process.
• Embodiments of the ferritic stainless steels and comparative reference steels were made in the laboratory with the compositions set forth in Table 1 below.
• Plant Material The materials identified as “Plant Material” were processed on production equipment in the plant according to the following parameters. Each slab was reheated to a temperature of 2273-2296° F. (1245-1258° C.). It was then hot rolled to a strip thickness of 0.200-0.180′′ (5.08-4.57 mm). The hot rolled strip was then hot band annealed to a temperature of 1950-2000° F. (1066-1083° C.). After cold rolling to 0.079-0.059′′ (2.0-1.5 mm), the strip was final annealed to a temperature of 1900-2000° F. (1038-1093° C.).
• HT #831187 is Type 444 stainless steel
• HT #830843 is 15 CrCb stainless steel, which is a product of AK Steel Corporation, West Chester, Ohio.
• the oxidation resistance of several of the steel compositions described in Example 1 and Table 1 above was tested at 930° C. for 200 hours in air. The results of the tests are set forth in Table 2 below. The individual compositions are each identified by their respective ID number. The oxidation resistance was evaluated two factors. One was the amount of weight gain, and the other was degree of spalling. For each material, except HT #920097, the reported weight gain value is an average of two tests. For HT #9200097, eight samples were tested and the minimum, average, and maximum of these eight tests has been reported.

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