US2076885A - Production of rustless iron - Google Patents

Production of rustless iron Download PDF

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US2076885A
US2076885A US728415A US72841534A US2076885A US 2076885 A US2076885 A US 2076885A US 728415 A US728415 A US 728415A US 72841534 A US72841534 A US 72841534A US 2076885 A US2076885 A US 2076885A
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manganese
chromium
slag
metal
bath
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Alexander L Feild
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Rustless Iron & Steel Corp
RUSTLESS IRON AND STEEL Corp
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21CPROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/04Making ferrous alloys by melting
    • C22C33/06Making ferrous alloys by melting using master alloys

Definitions

  • This invention relates to the manufacture of chromium-manganese irons and steels, and. especially to the manufacture of chromiumganese irons of high chromium and manganese contents and low carbon contents.
  • chromium-manganese irons and steels irons and steels analyzing approximately, chro- 10 mium 10% to 35%, manganese 6% to%, carbon .05% to .15% for the alloy iron and .l5% to 1% for the alloy steel, together with desired supple-'- mentary additions of nickel, copper, aluminum, silicon, molybdenum, tungsten and the like for 15 special purposes and with the usual low percentages of sulphur and phosphorus and the balance substantially iron), and especially to the simple, direct and'thoroughly reliable production of chromium-manganese irons, employing inexpensive g0 and readily available raw materials and utilizing known iurnacing and operating equipment.
  • the invention accordingly consists in the combination of elements, mixture of materials and composition of ingredients and in the several steps and the relation of each of the same to one or more of the others as described herein and the scope of the application of which is indicated in the following claims.
  • One of the outstanding objects of my invention is the production of high chromium high manganese irons and steels, and especially the production of austenitic chromium-manganese irons in a simple, direct and economical manner employing inexpensive and readily available raw materials in the most economical proportions depending upon the availability and fluctuations in current market prices, achieving high grade, sound, clean metal which may be manufactured and sold at a price considerably beneath that of the comparatively expensive chrominim-nickel irons and steels and which may be introduced into a wider range of applications supplanting known inferior but less expensive metals.
  • a material high in manganese content such as any one of the manganese ores, pyrolusite MnOz, manganite MnOCOHl, hausmannite MD304, braunite 3Mnz03, MnSiOs melted down in a suitable furnace with chrome ore FeOCrzO: and/or high carbon ferrochrome (produced by smelting this ore with coke and silica achieving a product analyzing approximately,
  • the large quantities of ore used are, preferably, thoroughly dried at a high temperature prior to charging into the furnace.
  • the pre-drying of the ores is carried out in any suitable manner, as by a long heating in a rotary gas-fired kiln at such temperatures as to rid the ores of substantially all free and combined moisture normally present.
  • predried materials eifectively minimizes the amount of moisture introduced into the furnace and consequently limits the amount of hydrogen available to contaminate the metal during melt-down, as a result of the decomposition of this moisture by the action of 'the electric furnace arcs, and to subsequently come out during solidification of the metal after teeming to cause gas-pockets and like defects, all as more particularly indicated in the Patent No. 1,925,916 granted to William Bell Amess on September 5, 1933 and entitled Process of producing alloys.
  • an electric arc furnace is preferably employed as a means of heating and furnacing the ingredients.
  • Heroult furnace or other furnace of the direct arc type, employing carbon or graphite electrodes and lined with chromite brick to a height somewhat above the slag line and having sidewalls and roof of silica brick is used in this practice.
  • the furnace Prior to charging the ingredients into the electric arc furnace, the furnace is preheated in any suitable manner, as by arcing the furnace on electrode butts or by means of a gas torch. After the furnace bottom and walls have been adequately preheated, the preheating means are withdrawn and the raw materials, indicated above, comprising the initial charge of ingredients for a heat of high chromium high manganese iron or steel are charged into the furnace.
  • Chromium in all of these forms is much less expensive than chromium as'the generally used low carbon ferrochrome.
  • manganese is least expensive in the form of manganese ore and progressively more expensive as manganese-containing scrap iron or steel, high carbon feromanganese and the generally used low carbon ferromanganese,
  • the additions of chromium and manganese may be largely made in the form of high carbon ferrochrome and high carbon ferromanganese respectively, or as high carbon ferrochrome-manganese, substituting in whole or in part for additions of chrome ore and manganese ore.
  • the use of great quantities of high carbon ferrochrome and high carbon feromanganese as sources of chromium and manganese is found to be appreciably more expensive than the use of substantial quantities of the ores of chromium and manganese for making these additions.
  • the amount of high chromium high manganese iron. and steel scrap employed as a source of chromium and manganese is generally determined by the availability of scrap metal in and around the melt shop and various customer example, the scrap available as ingot butts, crop ends, scrap sheet, punchings, clippings and the like amounts to from 40% to 50% of the metal tapped. This figure may even amount to some 60% or 70% where the sheet or strip is fabricated into various ultimate articles of manufacture,
  • the amounts of chromium and manganese present in the bath of metal at this stage of the process are largely dependent upon the amount of high chromium high manganese iron or steel scrap added to the charge (and the average chromium and manganese contents of this-scrap) and the amount of high carbon ferrochrome and high carbon ferromanganese melted down.
  • the quantities of chromium oxide and manganese oxide present in the, slag overlying the bath of metal are in a great measure dependent upon the amounts of' chrome ore and manganese ore present in the initial charge ofingredients.
  • the quantities of chromium and manganese appearing in the metal bath as the alloying elements, as compared with the amounts of chromium and manganese appearing in the slag as oxides of chromium and -manganese, are further dependent upon the oxidizing character of the slag overlying the metal bath and the tendency for this slag to oxidize these elements from the bath under the operating conditions encountered in practice.
  • the excessive. loss of chromium and manganese into the slag as oxides of these elements is effectively prevented, as appears more fully hereinafter, by conducting the'melting operation at a temperature of superheat and by initially proportioning relative amounts of chromium and manganese going to form the metal bath and the overlying slag.
  • the strongly oxidizing character of the slag blanket overlying the bath of metal throughout the period of melting down of the charge of ingredients is effective in oxidizing the carbon supplied the bath of metal by the low carbon steel scrap, the c romium-containing or manganesecontaining iron or steel scrap and the high carbon ferrochrome and the high carbon ferromanganese.
  • the practical difficulties in oxidizing car bon from the metal are greatly lessened where the chromium content of the bath is at a minimum.
  • the strongly oxidizing character of this slag furthermore acts-as an effective barrier between bath for this element.
  • the melting operation is preferably conducted at a high melt-down temperature.
  • These high operating temperatures which for convenience I designate as temperatures of superh'eat, furthermore assures a very active oxidation of carbon from the metal bath and the realization of an extremely low carbon product in a, minimum of time and with the consumption of a minimum of power.
  • a non-carbonaceous reducing agent such as ferrosilicon
  • ferrosilicon chemically in excess of the oxides of iron, chromium and manganese contained in the slag
  • the contamination of the metal .bath with the silicon of the reducing agent during this stage of the process is effectively prevented in spite of the use of the excessive quantities of silicon, by conducting the reduction under strongly basic slag conditions.
  • the desired basic conditions are preferably achieved by burnt lime in an amount of about three to five times the total silicon content of the ferrosiiicon employed. Burnt lime, preferably predried to free the lime of substan- 75 tially all free and combined moisture normally aoraeee present, is conveniently charged onto the slag along with the silicon-containing reducing agent.
  • the large quantities of burnt lime charged onto the slag overlying the bath of metal during the reducing period serve not only to render the slag strongly basic and prevent silicon contamination of the metal but also serve to give body to the slag (which is highly fluid and watery because of the large percentage of manganese oxide present in the slag) which in a manner not fully understood by me is effective in achieving a highly eflicient reduction of the reducible oxide content of the slag.
  • chrome ore and manganese ore are preferably charged along with the silicon reducing agent and burnt lime in corresponding 1 successive batches.
  • chrome ore and/or manganese ore at this stage of the process permits the use of a maximum quantity of these cheap sources of chromium and manganese (a feature particularly important in the production of high chromium high manganese irons and steels of the higher chromium and manganese analyses) while maintaining a manageable volume of slag within the furnace throughout both the melt down oxidation period and the subsequent reduction period with a minimum submersion of the furnace electrodes in the furnace of metal thereby limiting objectionable carbon pickup from the furnace electrodes throughout the complete process.
  • 2,500 pounds of chrome ore and 200 pounds of pyrolusitc (MnOz) are charged along with the ferrosilicon and lime.
  • burnt lime and chromium and manganese ores have been added and have fused and completed their reactions with the ingredients present in the slag and metal and a substantially complete recovery of the oxides of chromium and manganese contained in the slag is achieved, as evidenced by a change in color of successive samples taken from the furnace from a black to a light green or gray, the reduction stage of the process is at an end.
  • the slag overlying the bath of metal from which iron, chromium and manganese are completely recovered is then completely drawn off the metal.
  • a basic finishing slag of burnt lime and fine ferrosilicon is scattered over the exposed surface of the metal bath. (About 500 pounds of burnt lime and about '75 pounds of the 75% grade ferrosilicon are employed for the example given.)
  • the heating of the bath is continued at the reduced power input necessary to maintain the metal at a desired temperature until the refining of the metal is completed.
  • the necessary duration of the refining period is greatly decreased in the production of high chromium high manganese steels because of thepresence of a large percentage of manganese in the metal which is effective in refining and cleansing the metal of distributed oxides.
  • lump ferrosilicon is added as desired to adjust the final silicon content of the metal. In the example given, about 50 pounds of 7% f errosilicon is used to make the 'flnal adjustment of the silicon content of the metal.
  • the furnace electrodes are raised and the heat of metal is tapped into a ladle for teeming.
  • the metal is clean, sound and comparatively free of objectionable oxide inclusions.
  • the process is particularly favorable to obtaining a desired economic balance between the raw materials employed as sources of the alloy metals, chromium and manganese, by relatively adjusting the proportions of ingredients (to such an extent as is consistent with the maintenance of good furnace operating conditions) chromium,- manganese'iron or steel scrap, chrome ore and high carbon ferromanganese, in accordance with variations in the availability of these materials and the fluctuations in their market prices.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Description

Patented Apr. 13, 1937 UNITED STATES PATENT OFFICE 2,016,885 tm i fifll iillffil 1,,
meme assignments, to Rostlcss Iron and Steel Corporation, Balflmore, MIL, a corporation of Delaware No Drawing. application May or, 1934, Serial 9 Claims This invention relates to the manufacture of chromium-manganese irons and steels, and. especially to the manufacture of chromiumganese irons of high chromium and manganese contents and low carbon contents.
Among the objects of my invention is the emcient, economical and thoroughly practical production of chromium-manganese irons and steels (irons and steels analyzing approximately, chro- 10 mium 10% to 35%, manganese 6% to%, carbon .05% to .15% for the alloy iron and .l5% to 1% for the alloy steel, together with desired supple-'- mentary additions of nickel, copper, aluminum, silicon, molybdenum, tungsten and the like for 15 special purposes and with the usual low percentages of sulphur and phosphorus and the balance substantially iron), and especially to the simple, direct and'thoroughly reliable production of chromium-manganese irons, employing inexpensive g0 and readily available raw materials and utilizing known iurnacing and operating equipment.
The invention accordingly consists in the combination of elements, mixture of materials and composition of ingredients and in the several steps and the relation of each of the same to one or more of the others as described herein and the scope of the application of which is indicated in the following claims.
As conducive to a. clearer understanding of certain features of my invention it may be noted at this point that in various marine, aviation, automotive, industrial and architectural applications where a bright surface pleasing to the eye and. resistant to the corrosive attack of various acid, alkali or salt atmospheres or solutions is required, or where metal which is strong, tough. and durable and resistant to the corrosive attack of. various acids, alkalies and salts at high temperatures is required, the well known austenitic chromium-nickel irons and steels are in widespread use at the present time. The extent of the use of such alloy irons and steels is greatly handicapped, however, by the comparative great expense of these materials as compared with ordinary irons and steels which are less attractive to the eyeand which are less resistant to corrosive attacks of the atmosphere or various acid, alkali and salt mediums.
While numerous substitutes have been proposed for the expensive austenitic chromium-nickel irons and steels the only alloy iron or steel which has gained any present-day favor is the chromium-manganese iron or steel, the general analysis of which is indicated above.
In the production of chromium-manganese irons and steels, and particularly in the productlon of the high chromium high manganese irons and steels, which are largely austenitic in structure, in accordance with heretofore known and/or used methods of production the expensive sources 5 of chromium and manganese, are added to a bath of low carbon iron maintained at a desired temperature. Such methods of production, while simple in procedure, require prolonged heating with a continuous consumption of power and yield a very expensive product, largely because of the great expense of the raw materials used in obtaining the alloying additions, chromium and manganese.
While known methods of producing chromiummanganese irons and steels are ordinarily satisfactory in the production of the usual low chrolow manganese alloys these methods as applied to the production of high chromium high manganese austenitic irons and steels render the 20 product prohibitively expensive. In fact, the cost of producing the austenitio chromium-manganese irons and steels in accordance with known andfor used methods is so great that the margin of savings over the production of the well-known 25 austenitic chromium-nickel irons and steels is so small that there is little incentive to replace, for general purposes, these costly irons and steels with the chromium-man ganese irons and steels.
One of the outstanding objects of my invention, therefore, is the production of high chromium high manganese irons and steels, and especially the production of austenitic chromium-manganese irons in a simple, direct and economical manner employing inexpensive and readily available raw materials in the most economical proportions depending upon the availability and fluctuations in current market prices, achieving high grade, sound, clean metal which may be manufactured and sold at a price considerably beneath that of the comparatively expensive chrominim-nickel irons and steels and which may be introduced into a wider range of applications supplanting known inferior but less expensive metals.
In the practice of my invention a material high in manganese content, such as any one of the manganese ores, pyrolusite MnOz, manganite MnOCOHl, hausmannite MD304, braunite 3Mnz03, MnSiOs melted down in a suitable furnace with chrome ore FeOCrzO: and/or high carbon ferrochrome (produced by smelting this ore with coke and silica achieving a product analyzing approximately,
60% to 70% chromium, 4% to 7% carbon, 20% to 30% iron) and a desired quantity of available low carbon steel scrap, either with or without a readily available amount of high chromium high manganese iron or steel scrap or straight chr0- 10 mium rustless iron or steel scrap or high manganese iron or steel scrap, and a suiilcient quantity of an oxidizing agent, such as roll scale or magnetic iron ore concentrate to exclude and/or remove carbon from the ingredients, thereby forming a bath of ferrous metal containing manganese and chromium with an overlying oxidizing slag rich in the oxides of chromiumand manganese.
To assure the production of sound metal, free from gas-pockets, pits and the like, the large quantities of ore used are, preferably, thoroughly dried at a high temperature prior to charging into the furnace. The pre-drying of the ores is carried out in any suitable manner, as by a long heating in a rotary gas-fired kiln at such temperatures as to rid the ores of substantially all free and combined moisture normally present.
The use of predried materials eifectively minimizes the amount of moisture introduced into the furnace and consequently limits the amount of hydrogen available to contaminate the metal during melt-down, as a result of the decomposition of this moisture by the action of 'the electric furnace arcs, and to subsequently come out during solidification of the metal after teeming to cause gas-pockets and like defects, all as more particularly indicated in the Patent No. 1,925,916 granted to William Bell Amess on September 5, 1933 and entitled Process of producing alloys.
40 In order to achieve temperatures sufliciently high to effectively melt the refractory ingredients comprising the charge, an electric arc furnace is preferably employed as a means of heating and furnacing the ingredients. Conveniently,
a Heroult furnace, or other furnace of the direct arc type, employing carbon or graphite electrodes and lined with chromite brick to a height somewhat above the slag line and having sidewalls and roof of silica brick is used in this practice.
Prior to charging the ingredients into the electric arc furnace, the furnace is preheated in any suitable manner, as by arcing the furnace on electrode butts or by means of a gas torch. After the furnace bottom and walls have been adequately preheated, the preheating means are withdrawn and the raw materials, indicated above, comprising the initial charge of ingredients for a heat of high chromium high manganese iron or steel are charged into the furnace. In the production of a heat of high chromium high manganese iron or steel to a desired specification of chromium, manganese and carbon contents (with or without one or more supplementary additions of nickel, copper, aluminum, silicon, molybdenum, tungsten, vanadium and the like in specified amounts), the relative amounts of chromium contributed by the chromium-containing iron or steel scrap, high carbon ferrochrome and chrome ore, and the relative amounts of manganese contributed by the manganese-containing iron or steel scrap, high carbon ferromanganese and manganese ore, all as used in proportions consistent with good furnace operating conditions, are largely determined by the availability of these various ingredients and the reaoraaae spective current market prices. Ordinarily the contained chromium is least expensive in the form of chrome ore, is more expensive in the form of chromium-containing iron or steel scrap and is most expensive as high carbon ferrochrome.
. Chromium in all of these forms, however, is much less expensive than chromium as'the generally used low carbon ferrochrome. Similarly, manganese is least expensive in the form of manganese ore and progressively more expensive as manganese-containing scrap iron or steel, high carbon feromanganese and the generally used low carbon ferromanganese,
To achieve clean, sound, high grade metal at a minimum of expense, a maximum of the less expensive chromium-containing and manganesecontaining ingredients as is consistent with good furnace operating conditions (greatly limited by the permissible volume of slag which may be handled) is therefore employed. Now, since the chromium-bearing ingredients are considerably more expensive than the manganese-containing materials, and since the cost differential between chrome ore and high carbon ferrochrome is appreciably greater than that between manganese ore and high carbon ferromanganese a maximum of the inexpensive chrome ore is preferably used in the practice of my invention.
Where the practice indicates that further volumes of slag may be adequately handled, as in the production of the high chromium high manganese irons and steels of the lower ranges of chromium and manganese contents, much of the addition of manganese may be made in the form of the inexpensive manganese ore. Practice has shown, however, that unsatisfactory furnac ing conditions are encountered where the chromium and manganese additions are made by chrome ore and manganese ore respectively, as for example, in the production of the high chromium high manganese irons and steels of a medium range of analyses.
Highly satisfactory results are achieved in the production of high grade, inexpensive metal by employing a maximum of chrome ore for the chromium addition and the readily available high carbon ferromanganese as the source of manganese. In many instances, as in the production of the high chromium high manganese irons and steels of the upper analyses ranges of chromium and manganese, much of the chromium is added in the form of high carbon ferrochrome.
Where desired the additions of chromium and manganese may be largely made in the form of high carbon ferrochrome and high carbon ferromanganese respectively, or as high carbon ferrochrome-manganese, substituting in whole or in part for additions of chrome ore and manganese ore. Under present market conditions, however, the use of great quantities of high carbon ferrochrome and high carbon feromanganese as sources of chromium and manganese is found to be appreciably more expensive than the use of substantial quantities of the ores of chromium and manganese for making these additions.
In the practice of my process for producing high chromium high manganese irons and steels the amount of high chromium high manganese iron. and steel scrap employed as a source of chromium and manganese (as contrasted with the high manganese steel scrap-10% manganese, 1% carbon and the balance iron--which is well known and readily available) is generally determined by the availability of scrap metal in and around the melt shop and various customer example, the scrap available as ingot butts, crop ends, scrap sheet, punchings, clippings and the like amounts to from 40% to 50% of the metal tapped. This figure may even amount to some 60% or 70% where the sheet or strip is fabricated into various ultimate articles of manufacture,
such as machine or burner parts, kitchen ware,
automobile trim, architectural applications and similar products.
While as an economical measure the amount of high chromium high manganese iron or steel scrap employed in the production of a heat of metal is proportional to that rendered available about the melt shop, this amount may be greatly increased where large quantities of this scrap are available at a favorable market price andsimilarly, the amount of scrap employed may be greatly lessened, or omitted entirely, where an acute shortage of scrap is encountered or where the market price of scrap becomes excessive.
The highly flexible nature of my process of producing high chromium high manganese irons and steels assures the production of high grade metal at a minimum of expense by using a maximum of inexpensive raw materials, the relative proportions of which are varied as desired to meet fluctuating conditions of availability and market price.
As illustrative of the practice of my invention,
in the production of a heat of high chromium high manganese iron to a desired specification of chromium 17.0% to 19%, manganese 8% to 10%, usual silicon, sulphur and phosphorusrand 5 the balance iron, 4,000 pounds of low carbon steel scrap, 6,700 pounds of chromium manganese iron scrap (having an average analysis of chromium 17.5% manganese 10.0%, carbon .12% and the balance substantially iron), 3,000 pounds of chrome ore (48% CraOs), 800 pounds of high carbon ferrochrome (analyzing 4% to 6% carbon, 10% chromium and the balance iron), 2,500 pounds of ferromanganese (analyzing 6% to 8% carbon, 80% manganese and the balance iron),
and 4,000 pounds of roll scale, are charged onto the bottom of a chromite lined 6-ton threephase Heroult electric arc furnace rated 25 cycles, 120 to 180 volts, 2500 kva. preheated as indicated above.
Alternating current electrical energy is sup-- plied the furnace and the charge of ingredients begins to melt down forming individual pools of ferrous metal containing carbon, chromium and manganese immediately beneath the furnace G5 electrodes. Under the continuing action of the intense heat of the electric furnace arcs the melting charge of ingredients soon forms a single bath of ferrous metal containing considerable quantitles of chromium and manganese and appreciable quantities of carbon as indicated above,
covered by a fluid overlying blanket of slagstrongly oxidizing in character and rich in the oxides of manganese and chromium.
It may be noted at this point that the presence of considerable quantities of manganese oxides in the blanks: of slag overlying the bath of metal renders the lag fluid and permits .asmoother furnace operation with a minimum of dipping of the furnace carbon or graphite electrodes into the slag and metal and with a consequent minimization of the amount of carbon directly contributed to the metal bath. This is a feature of considerable practical importance where the elimination of carbon requires the use of additional materials and the expenditure of much time and effort.
The amounts of chromium and manganese present in the bath of metal at this stage of the process are largely dependent upon the amount of high chromium high manganese iron or steel scrap added to the charge (and the average chromium and manganese contents of this-scrap) and the amount of high carbon ferrochrome and high carbon ferromanganese melted down. Likewise, the quantities of chromium oxide and manganese oxide present in the, slag overlying the bath of metal are in a great measure dependent upon the amounts of' chrome ore and manganese ore present in the initial charge ofingredients.
The quantities of chromium and manganese appearing in the metal bath as the alloying elements, as compared with the amounts of chromium and manganese appearing in the slag as oxides of chromium and -manganese, are further dependent upon the oxidizing character of the slag overlying the metal bath and the tendency for this slag to oxidize these elements from the bath under the operating conditions encountered in practice. The excessive. loss of chromium and manganese into the slag as oxides of these elements is effectively prevented, as appears more fully hereinafter, by conducting the'melting operation at a temperature of superheat and by initially proportioning relative amounts of chromium and manganese going to form the metal bath and the overlying slag.
The strongly oxidizing character of the slag blanket overlying the bath of metal throughout the period of melting down of the charge of ingredients is effective in oxidizing the carbon supplied the bath of metal by the low carbon steel scrap, the c romium-containing or manganesecontaining iron or steel scrap and the high carbon ferrochrome and the high carbon ferromanganese. The practical difficulties in oxidizing car bon from the metal are greatly lessened where the chromium content of the bath is at a minimum. Under these conditions of operation, as where the major portion of the chromium of the metal is supplied by chrome ore, appearing in this stage of the process in the slag overlying the bath of metal, and where the manganese content is largely supplied by manganese-containing scrap and high carbon ferromanganese directly appearing in the ferrous metal 'bath as a desired alloying addition, the tendency. for the bath of metal to pick up carbon from the electrodes is reduced to a minimum since manganese does not have the thirst for carbon that is characteristic of chromium.
The strongly oxidizing character of this slag furthermore acts-as an effective barrier between bath for this element.
In order to minimize the oxidation of chromium and manganese from the metal bath incident to the removal and/or exclusion of carbon, the melting operation is preferably conducted at a high melt-down temperature. The use of these high operating temperatures, which for convenience I designate as temperatures of superh'eat, furthermore assures a very active oxidation of carbon from the metal bath and the realization of an extremely low carbon product in a, minimum of time and with the consumption of a minimum of power.
While no reliable method is known to me for precisely determining the temperatures of metal and slag during the melt-down period, it is estimated that these temperatures are from about 3100 F. to 3250" F., which is some 150 to 300 F.
higher than those ordinarily encountered in ordinary electric steel making practices. The use of such extremely high operating temperatures is permitted, as indicated above, by the highly re- 1 fractory nature of the chromite brick furnace lining employed.
The excessive oxidation of chromium and manganese from the metal bath, which is ordinarily incidental to the oxidation of carbon, is further lessened by the inhibiting effect of the large quantities of chromium and manganese present in the slag as oxides of chromium and manganese. The tendency toward the oxidation of these alloying elements from the molten metal is greatly lessened by the initially high balance between the molten chromium and manganese oxides in the slag overlying the metal and the oxides of chromium and manganese dissolved in the metal. In this manner certain further savings are realized 3:; in material and labor required to recover chromium and manganese from the slag, as more particularly described hereinafter, thereby achieving a highly eflicient and economical process.
When the charge of ingredients is completely melted down and samples taken from the bath for purposes of analysis indicate that the carbon content is several points below the maximum value permissible the melt-down period is at an end. At this stage of the process, there are available in the slag great quantities of iron, chromium and manganese in the form of oxides of these metals, although much of the iron oxide in the slag has been lost during the melt-down oxidation period in removing and/or excluding carbon from the melting metal and in the oxidation of chromium and manganese incidental to the oxidation of carbon, all as more particularly described above.
The large quantities of metal which are found in the slag as oxides at this stage of the process, are recovered in a reducing period, where preferably a non-carbonaceous reducing agent, such as ferrosilicon, chemically in excess of the oxides of iron, chromium and manganese contained in the slag, is charged onto the slag overlying the bath of metal. The precise amount of reducing agent required to effect a high recovery of the metals from the slag is ordinarily determined empirically.
The contamination of the metal .bath with the silicon of the reducing agent during this stage of the process is effectively prevented in spite of the use of the excessive quantities of silicon, by conducting the reduction under strongly basic slag conditions. The desired basic conditions are preferably achieved by burnt lime in an amount of about three to five times the total silicon content of the ferrosiiicon employed. Burnt lime, preferably predried to free the lime of substan- 75 tially all free and combined moisture normally aoraeee present, is conveniently charged onto the slag along with the silicon-containing reducing agent.
For the illustrative charge of ingredients set. forth above 2,500 pounds of crushed ferrosilicon of the 75% grade and 8,000 pounds of predried burnt lime are charged onto the slag overlying thebath of metal.
Prior to charging the silicon reducing agent and lime onto the slag, these ingredients are conveniently mixed on'the floor of the melt shop. This mixture is then charged onto the slag overlying the bathof metal from time to time as furnace conditions permit. By charging a large proportion of burnt lime along with the reducing agent in this manner the maintenance of strongly basic slag conditions during the reducing stage of the process is assured.
By carrying out the reduction of the oxides contained in the slag under strongly basic conditions silicon contamination of the metal is precluded. The acid silicates resulting from the reduction of the reducible oxides of the slag by the silicon reducing 'agent employed react with the basic lime added to the slag and form a series of calcium silicates, all as more particularly described in the Patent No. 1,932,252 of William B. Arness, granted October 24, 1933 and entitled Process of producing alloys. These calcium silicates are among the most stable components of s the slag.
The large quantities of burnt lime charged onto the slag overlying the bath of metal during the reducing period, as more particularly described above, serve not only to render the slag strongly basic and prevent silicon contamination of the metal but also serve to give body to the slag (which is highly fluid and watery because of the large percentage of manganese oxide present in the slag) which in a manner not fully understood by me is effective in achieving a highly eflicient reduction of the reducible oxide content of the slag.
The continued heating of the metal and slag during the prolonged reducing period affords an opportunity to melt down further quantities of chrome ore and manganese ore. These materials are preferably charged along with the silicon reducing agent and burnt lime in corresponding 1 successive batches. The addition of chrome ore and/or manganese ore at this stage of the process permits the use of a maximum quantity of these cheap sources of chromium and manganese (a feature particularly important in the production of high chromium high manganese irons and steels of the higher chromium and manganese analyses) while maintaining a manageable volume of slag within the furnace throughout both the melt down oxidation period and the subsequent reduction period with a minimum submersion of the furnace electrodes in the furnace of metal thereby limiting objectionable carbon pickup from the furnace electrodes throughout the complete process. Illustratively, 2,500 pounds of chrome ore and 200 pounds of pyrolusitc (MnOz) are charged along with the ferrosilicon and lime.
After all of the reducing agent, burnt lime and chromium and manganese ores have been added and have fused and completed their reactions with the ingredients present in the slag and metal and a substantially complete recovery of the oxides of chromium and manganese contained in the slag is achieved, as evidenced by a change in color of successive samples taken from the furnace from a black to a light green or gray, the reduction stage of the process is at an end. The slag overlying the bath of metal from which iron, chromium and manganese are completely recovered is then completely drawn off the metal.
A basic finishing slag of burnt lime and fine ferrosilicon is scattered over the exposed surface of the metal bath. (About 500 pounds of burnt lime and about '75 pounds of the 75% grade ferrosilicon are employed for the example given.) The heating of the bath is continued at the reduced power input necessary to maintain the metal at a desired temperature until the refining of the metal is completed. The necessary duration of the refining period is greatly decreased in the production of high chromium high manganese steels because of thepresence of a large percentage of manganese in the metal which is effective in refining and cleansing the metal of distributed oxides. During this period lump ferrosilicon is added as desired to adjust the final silicon content of the metal. In the example given, about 50 pounds of 7% f errosilicon is used to make the 'flnal adjustment of the silicon content of the metal.
After the desired refining of the metal is effected the application of power to the furnace is discontinued, .the furnace electrodes are raised and the heat of metal is tapped into a ladle for teeming. There is produced about 18,200 pounds of high chromium high manganese iron ingots analyzing approximately, .07% carbon, 17.2% chromium, 9.8% manganese, .50% silicon with the usual percentages of sulphur and phosphorus and the balance substantially iron. The metal is clean, sound and comparatively free of objectionable oxide inclusions.
Where desired supplementary additions of nickel, copper, aluminum, silicon, molybdenum, tungsten, vanadium, zirconium and the like may 40 be made in accordance with standard practice either in the furnace or in the ladle.
The production of high chromium high man- 'ganese irons and steels with a minimum repair and/or replacement of furnace linings and a 45 minimum furnace shut-down and loss of operating time, is enjoyed by virtue of the chromite lining employed. This lining, as compared to heretofore known and/or used linings, is particularly resistant to destructive attack, at the 5 high temperatures employed, by the oxidizing melt-down slag followed by the reducing slag used in the second stage of the process, all as more particularly pointed out in my Patent No.
1,925,182, granted September 5, 1933 and entitled 55 Process for the manufacture of rustless iron. The
impervious nature of this material limits the absorption of iron and manganese oxides during the melt-down period and the consequent direct attack upon the furnace lining by a reduction of 60 these oxides during the reducing period, a procedure exceedingly destructive to the lining at the slag line. That part of the bottom and sidewalls which is eroded by metal and slag goes into the slag from which the reducible oxides are effectively recovered, supplying iron and chromium to the bath of metal, thus, in a measure, compensating for the cost of the erosion of the lining.
Thus, it will be seen that there has been 70 provided in this invention an art of producing high chromium high manganese irons and steels and especially the production of high chromium high manganese irons (metal in which the carbon content ranges as indicated above, from 75 about .05% to in which the various objects reduce chromium oxides, larger quantities of the inexpensive source of chromium, chrome ore, are effectively used without risking the production of dirty metal, objectionably contaminated with oxides.
It will be further seen that the process is particularly favorable to obtaining a desired economic balance between the raw materials employed as sources of the alloy metals, chromium and manganese, by relatively adjusting the proportions of ingredients (to such an extent as is consistent with the maintenance of good furnace operating conditions) chromium,- manganese'iron or steel scrap, chrome ore and high carbon ferromanganese, in acordance with variations in the availability of these materials and the fluctuations in their market prices.
While as illustrative of the practice of my invention substantial quantities of chrome ore and manganese ore are added both along with the initial charge of ingredients melted down and with the reducing agent added after melt-down is complete, in order to take advantage of the comparatively long melt-down and reduction periods to eifect a thorough heating of these refractory ingredients, it will be understood that chrome ore and/or manganese ore may be added while the melt-down period is in progress, especially toward the end of this period when samples of metal have been taken and the heat of metal is being held in the furnace awaiting a report of the carbon analysis, in order to realize the benefits of the available furnace heat during this period. Likewise, it will be understood that where furnacing conditions permit substantially all of the ore may be added during the melt-down period, thus in a measure simplifying the procedure.
As many possible embodiments may be made of my invention'and as many changes may be made in the embodiments hereinbefore set forth, it will be understood that all matter described herein is to be interpreted as illustrative and not in a limiting sense.
I claim:
1. In the production of high manganese rustless irons and steels in an electric arc furnace, the art which includes, melting down in said furnace iron scrap, a material rich in manganese, a material rich in chromium and an oxidizing agent thereby forming a bath of ferrous metal containing chromium and manganese covered by an oxidizing slag containing oxides of manganese and. chromium, and after melt-down is complete reducing the oxides contained in said slag thereby effecting an enrichment of the bath in manganese and chromium.
2. In the production of high manganese rustless irons and steels in an electric arc furnace, the art which includes, melting down in said furnace iron scrap, manganese ore, high carbon ferrochrome and an oxidizing agent thereby forming a bath of ferrous metal containing chromium and manganese covered by an oxidizing slag containing oxides of manganese and chromium, and
after melt-down is complete reducing the oxides contained in said slag thereby effecting an enrichment of the bath in manganese and chromium.
3. In the production of high manganese rustless irons and steels in an electric arc furnace, the art which includes, melting down in said furnace iron scrap, manganese ore and chrome ore thereby forming a bath of metal covered by a slag 10 containing the oxides of manganese and chromium, and after melt-down is complete reducing the oxides contained in said slag thereby supplying manganese and chromium to said bath.
4. In the production of high manganese rust- 15 less irons and steels in an electric arc furnace,
the art which includes, melting down in said furnace iron scrap, amaterial rich in manganese, a material rich in chromium and an oxidizing agent thereby forming a bath of ferrous metal 2 containing chromium and manganese covered by an oxidizing slag containing oxides of manganese and chromium, bringing said bath of metal and the overlying blanket of slag up to a temperature of superheat thereby oxidizing and/or ex- 25 eluding carbon from said bath, and after meltdown is complete and a desired low carbon content of the bath is reached reducing the oxides of chromium and manganese contained in said slag thereby efiecting an enrichment of the metal 30 bath.
5. In the production of high manganese rustless irons and steels in an electric arc furnace, the art which includes, melting down in said furnace iron scrap, a material rich in manganese 35 from which substantially all normal moisture is removed, a material rich in chromium from which substantially all normal moisture is removed and an oxidizing agent thereby forming a bath of ferrous metal containing chromium 40 and manganese covered by an oxidizing slag containing oxides of manganese and chromium, and after melt-down is complete reducing the oxides of manganese and chromium contained in said slag under strongly basic conditions 45 thereby efiecting an enrichment of the bath in manganese and chromium.
6. In the production of high manganese rustless irons and steels in an electric arc furnace, the art which includes, melting down a material 5 rich in manganese, a material rich in chromium and an oxidizing agent in the presence of a pool of ferrous metal thereby forming a bath of ferfecting an enrichment of the bath in manganese and chromium.
7. In the production of high manganese rustless irons and steels in an electric arc surface, the art which includes, melting down in said furnaceiron scrap, a material rich in manganese, a material rich in chromium and an oxidizing agent thereby forming a bath of ferrous metal containing chromium and manganese covered by an oxidizing slag containing oxides of manganese and chromium and after melt-downis complete charging a silicon reducing agent and chrome ore onto the slag overlying said bath thereby reducing the oxides contained in the slag and eflecting an enrichment of the bath in manganese and chromium.
8. In the production of high manganese rustless irons and steels in an electric arc furnace, the art which includes, melting down in said furnace low carbon iron scrap, high manganese rustless iron scrap, a material rich in manganese, a material rich in chromium and an oxidizing agent thereby forming a bath of ferrous metal containing chromium and manganese covered by an oxidizing slag containing oxides ganese and chromium, and after melt-down is complete charging a silicon reducing agent and burnt lime onto the slag overlying said bath thereby reducing the oxides contained in said slag under basicconditions and effecting an enrichment of the bath in manganese and chromium.
ALEX. L. FEILD.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2430131A (en) * 1944-11-04 1947-11-04 American Rolling Mill Co Production of stainless steel
US2800406A (en) * 1953-11-10 1957-07-23 Union Carbide Corp Process for making manganese-bearing steels
WO2009076923A3 (en) * 2007-12-14 2009-08-13 Salzgitter Flachstahl Gmbh Method for producing a steel melt containing up to 30% of manganese
US10125413B2 (en) * 2013-12-17 2018-11-13 Outotec (Finland) Oy Method for producing manganese containing ferroalloy

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2430131A (en) * 1944-11-04 1947-11-04 American Rolling Mill Co Production of stainless steel
US2800406A (en) * 1953-11-10 1957-07-23 Union Carbide Corp Process for making manganese-bearing steels
WO2009076923A3 (en) * 2007-12-14 2009-08-13 Salzgitter Flachstahl Gmbh Method for producing a steel melt containing up to 30% of manganese
CN101896625A (en) * 2007-12-14 2010-11-24 萨尔茨吉特法特尔有限公司 Method for producing a steel melt containing up to 30% of manganese
US20110094336A1 (en) * 2007-12-14 2011-04-28 Salzgitter Flachstahl Gmbh Method for producing a steel melt containing up to 30% manganese
DE102007061062B4 (en) * 2007-12-14 2012-08-02 Peiner Träger GmbH Process for producing a steel melt containing up to 30% manganese
RU2476604C2 (en) * 2007-12-14 2013-02-27 Зальцгиттер Флахшталь Гмбх Method for obtaining molten steel with manganese content of up to 30%
US8444743B2 (en) 2007-12-14 2013-05-21 Salzgitter Flachstahl Gmbh Method for producing a steel melt containing up to 30% manganese
CN101896625B (en) * 2007-12-14 2013-06-12 萨尔茨吉特法特尔有限公司 Method for producing a steel melt containing up to 30% of manganese
AU2008338104B2 (en) * 2007-12-14 2013-09-19 Peiner Traeger Gmbh Method for producing a steel melt containing up to 30% of manganese
EP2242862B1 (en) 2007-12-14 2016-08-31 Salzgitter Flachstahl GmbH Method for producing a steel melt containing up to 30% of manganese
US10125413B2 (en) * 2013-12-17 2018-11-13 Outotec (Finland) Oy Method for producing manganese containing ferroalloy

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