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By Werner Schwartz, Wolfgang Haase

Lead sulfide concentrates, which may include other lead concentrates, are sintered on an up-draught sintering machine without the addition of any diluting agents or fluxes. Subsequently they are melted in an oil- or gas-fired rotary furnace. The sintering and melting processes are based upon the following roast-reaction: PbS + 2 PbO = 3 Pb + SO, PbS + PbSO, =2 Pb + 2 SO, For obtaining a lead bullion free from sulfur, the sintering process is carried out in such a way that the sinter product contains a small amount of excess oxygen above that to react with the sulfides. At the end of the melting process, when the reactions are finished, the remaining small amount of oxide residues is reduced with coal to which a certain percentage of soda ash (about 1 pct of the lead bullion) is added. For the lead smelting process described neither coke nor fluxes—except soda ash—are required. This process is being utilized by a European smelter successfully and with a high lead recovery. The consumption figures for the smelting of 100 tons per day of lead concentrates are indicated. The lead content of the lead concentrates from modern ore dressing plants ranges from 65 pct to above 80 pct. In most lead smelters of the world these concentrates are smelted in a blast furnace. For blast-furnace smelting the concentrates have to be desulfurized and agglomerated by sintering. A requirement for the perfect operation of a down-draught sintering machine and of a blast furnace is a maximum lead content in the feed of 40 to 45 pct. For this reason, some lead concentrates have to be diluted by adding return slags, limestone, and possibly iron oxide and sand. As an example, 100 tons of lead concentrate with 72 pct Pb would contain 13.5 tons of gangue (including the zinc). To produce a perfect sinter with 42 pct Pb it would be necessary to add 70 tons of flux and return slag, more than five times the original weight of the gangue, to the sinter mix and blast-furnace charge. A correspondingly large amount of coke would be required in order that all of these materials reach the heat of formation and the melting temperatures of the slag (1200" to 1400°C) inside the blast furnace. The roast-reaction process presents a possibility for lead recovery without dilution of the concentrates. In this process the concentrate mixed with coal is placed upon a Newnam-hearth and air is blown through nozzles into the heated mix. AS a result metalllic lead and a relatively great amount of so-called .'Grey Slag" with a lead content of 25 to 35 pct are formed. The slag is sintered to eliminate sulfur and, after addition of the requisite fluxes, treatt:d in a blast furnace. Owing to the poor recovery of lead from the hearths and to the unavoidable heavy hand-work plus the risk of poisoning this process is utilized in very few 112ad smelters today. Since in mxny countries of the world coke is expensive and difficult to obtain, it appeared feasible to use the principle of the roast-reaction by modern sintering and melting methods with recovery of the lead in electric, or oil, gas, or coal-fired furnaces. Two processes are utilized on an industrial scale: A) Lead smelting in the electric furnace of the Bolidens Gruv A/B in Sweden, as described by S. J. Walldcn, N. E. Lindvall, K.G. Gorling, and S. Lundquist. B) The self-fluxing lead smelting of Lurgi Gesell-schaft fiir Chemie und Huttenwesen m.b. H., Frankfurt a M, Germany, which is described in this paper. In the Boliden process referred to above the sinter mix is pelletized by enveloping return fines with layers of flue dust, limestone powder, and dried galena concentrate. The roasting and agglomeration are carried out on a down-draught machine, and a slight excess of sulfur is left in the sinter product. During the smelting in the electric furnance the roast-reactions occur and a slag poor in lead and a sulfur bearing lead are formed. This latter is subsequently oxidized in a converter to obtain lead bullion and dross. The Lurgi-process achieves the maximum possible extent of the roasting reaction on the sintering machine. The wet flotation concentrates are blended with return fines (lead content 70 to 80 pet), any existing flue dusts and lead slimes—but without the

Jan 1, 1962

By D. J. Carney, E. C. Rudolphy

IT has been demonstrated that inclusion size, distribution, and composition affect the machin-ability of resulphurized steels. Merchant and Zlatinl concluded that large sulphide inclusions aided machining by forming a (lubricating) coating on the tool face. Boulger et al.² and Van Vlack³ noted that the size, distribution, and composition of the inclusions in the steel affected the machinability. Steel specimens containing large globular sulphide inclusions usually exhibited excellent cutting properties, while machinability was adversely affected by the presence of numbers of oxide-type inclusions. Consequently a thorough knowledge of all the factors which affect the inclusions in the final product is desirable. Since almost all the inclusions have their origin in liquid steel, it was necessary to begin a study of inclusions in free-machining steels by studying the inclusions and chemical segregation in the as-cast ingot. Very little information is available on the size, distribution, shape, and composition of inclusions in large, capped, free-machining steel ingots, particularly the B1113 grade. Gregory and Whiteley4 made a general study of the inclusions in a small, high sulphur, free-machining steel ingot. Also, numerous authors have described the solidification and segregation characteristics of the four basic types of steel ingots, namely, rimmed, capped,7 semikilled,7,8 and killed7,9,10 ingots. Most of these studies were made with plain carbon or low alloy, low sulphur steel. It was desirable to study not only the ingot but also the change in size, shape, and number of inclusions on rolling an ingot to a bloom and thence to a billet. This procedure was followed and it is hoped that this study may serve the dual purpose of adding to the general knowledge of ingot solidification as well as contributing to the knowledge of the size, shape, distribution, and composition of inclusions from the ingot to the billet in a high sulphur, free-machining steel. Procedure A 12.000-lb 23x35x75 in. slab ingot of the B1113 grade was cast, sectioned, and studied both macro-scopically and microscopically. An adjacent ingot from the same heat and of the same size was rolled to a 77/8x77/8 in. bloom and thence to a 21/2x21/2 in. billet. These various bloom and billet sections were also sectioned and studied macroscopically and microscopically. Sectioning the Ingot: The ingot herein described was obtained from the United States Steel Corp.'s South Works Bessemer Blow No. 0193, a B1113 mechanically capped heat. The 23x35 in. ingot (No. 2) was teemed according to normal procedures and after stripping and transportation to the rolling mill was not placed in the soaking pit but allowed to air cool in an upright position. When completely solidified, the ingot was cut into sections by means of a powder scarfing torch and further sectioned by saw cutting as indicated in Fig. 1. Cut No. 2 (1x10x12 in.) from sections A through H was cleaned thoroughly, macroetched in a solution of 50-50 water and hot muriatic acid and used to obtain a macrograph of a horizontal section from the surface to slightly beyond the center of the 23-in. ingot dimension. Cuts No. 5 and 3 (lx81/2xl0 in. each) from sections A through H were treated in a similar manner to obtain a macrograph of a horizontal section from the surface to slightly beyond the center of the 35-in. ingot dimension. The composite macrograph of these horizontal ingot sections, which shows a vertical section of the ingot from top to bottom, is shown in Fig. 2. It should be noted that sections No. 2 are normal to sections 5 and 3 in the composite. Drillings for chemical analyses were obtained from selected positions within the above-mentioned ingot sections as noted in Fig. 3. The oxygen content was determined by the vacuum-fusion method. Samples for microscopic examination were cut from

Jan 1, 1954

By E. J. Dulis, R. M. Fisher, K. G. Carroll

IT is well known that ferritic steels containing more than 15 pct Cr when subjected to temperatures in the range of 700" to 1000°F exhibit increasing hardness and decreasing ductility. The phenomenon has been widely termed the "885 °F embrittlement," after the temperature of most marked effect.'.' In view of the excellent review articles available in the literature3-6 only a brief account of experimentally established facts need be given here. The extent of changes in physical characteristics during embrittlement depends on chromium concentration and time at temperature, higher alloy content and longer time both promoting more rapid and extensive changes. In a 27 pct Cr steel, changes in impact strength and in angle of fracture in bending can be detected after only a 1 hr exposure at 885°F; after 50 hr this steel becomes quite brittle. Hardness increases slowly with time during thousands of hours exposure and may attain a maximum hardness number twice as large as that of the unexposed steel. Microstructural changes accompanying embrittlement have been described as an initial widening of grain boundaries followed by eventual darkening of ferrite grains. Embrittled steels etch more readily, e.g., the weight loss of a 27 pct Cr steel in acid solution may occur at a rate one hundred fold greater following exposure at 885 OF. Marked changes which accompany embrittlement have been observed in electrical resistivity, specific gravity, and magnetic coercive force. Changes in physical properties may be readily removed by heating at temperatures above the embrittling range, such as a treatment at 1100°F for 1 hr. It has frequently been noted that the 885 °F embrittlement suggests precipitation on a submicro-scopic scale of a chromium-rich constituent, the nature of which has not been revealed by X-ray diffraction. Progressive broadening of the body-centered cubic diffraction lines during embrittlement has been observed," and recent observations by Lena and Hawkes' upon single crystals have shown early asterism in X-ray photographs, disappearing within an hour at 900 °F. Many workers have ascribed8-13 the phenomenon to a precipitation of a phase (FeCr), which is known to cause embrittling effects at temperatures much higher than 885°F. Two general observations, however. suggest that a precipitation cannot be responsible for the 885°F phenomenon: 1—prior cold work greatly enhances a formation, whereas it scarcely affects the 885 °F embrittlement, and 2—the presence of an alloying element such as nickel or manganese may have an effect on the 885 °F embrittlement which is opposed to its effect upon a formation. The slight enhancement of a formation and 885°F embrittlement observed in the presence of elements with strong carbide and nitride forming tendencies' is probably a consequence of lessened chromium depletion of the matrix. The bar graph in Fig. 1 shows a typical example, taken from two 27 pct Cr steels used in this work, of the hardness after exposure for 10,000 hr at 900°, 1050°, and 1200°F. Steel A (0.03 pct C, 3.13 pct Mn) showed marked hardening at 900" and 1200°F, whereas steel B (0.12 pct C, 0.63 pct Mn) exhibited only the 900°F hardening. The cr phase was found in steel A at the higher temperatures but not in steel B. Presumably a formation is enhanced by the low-carbon and high-manganese concentrations in A," Thus there are two distinctly different hardening phenomena present which cannot both be ascribed to v precipitation without invoking a transition phase possessing remarkable properties. Materials A number of chromium steels exposed for long periods (5000 to 34,000 hr) at 900°F, as well as unexposed samples of one of the steels, were available for this investigation. Table I gives the chemical compositions and aging treatments of these steels. In addition to these steels exposed in the elevated temperature test furnaces of the National Tube Division, a number of high-chromium steels were heated for short periods in small laboratory air furnaces and lead baths. Supplementing these commercial steels, a sample of high-purity (0.018 pct C, 0.002 pct N) 28 pct Cr iron, exposed 1000 hr at 887°F. was furnished by the Union Carbide and Carbon Corp. In addition, an alloy of iron and chromium of high purity containing 46 pct Cr was used. This

Jan 1, 1954

Jan 1, 1881

By HENRY COLEMAN

WE as employees of these related companies, I am sure, are proud to be affiliated with them, and have great faith in the sagacity and fore- sightedness of our employers. Most of us here have been called into important positions in these organizations, and it should be our most earnest endeavor to sense and carry them out as if they were our very own. We have been asked to supervise and carry on a work over which our employers cannot personally watch. It has been well said that the most efficient organization is that which requires the least attention from its head. Because of the very nature and condition of our work, which separates us by many miles from our employers and makes it impossible for us to receive attention and instructions from the heads of our departments, save for occasional visits and correspondence, we are given a great opportunity to prove that we can be efficient workers without too much attention from the heads of our departments. There are few employees who cannot do their duty when it is laid before them in specific terms, and when their employers are always there to see that their plans are carried out. But the employee who is really giving efficient service sees his duty himself and willingly does it. '

Jan 1, 1931

By R. E. Wagner

MISSOURI's famous lead area, in what is known as Southeast Missouri, is locally termed the "Lead Belt." These deposits are in the Bonne Terre dolomite of late Cambrian age which has a thickness of nearly 400 ft. Underlying this is the La Motte sandstone which varies in thickness from 0 to 400 ft. The La Motte beds are deposited directly on the ancient erosion surface of Pre-Cambrian porphyries and granites of probably Algonkian age. The buried igneous peaks extend up into the Bonne Terre in several areas within the Lead Belt. Overlying the Bonne Terre are shales and siliceous dolomites of late Cambrian and early Ordovician age. Within the Lead Belt these have a thickness of from 0 to 500 ft. The district is bounded in general on the southwest by the Sims Mountain fault, on the northwest and north by the Big River fault, and on the

Jan 1, 1947

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale forma¬tion) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. EXPERIMENTAL PROCEDURE Silver.-The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale formation) in alloys of silver with 2, 7 5, and 30 per cent of copper The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver' Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail 5,6 The present research confirms this anticipation The oxidation of a series of 20 dilute alloys of silver has been studied metallographically, some types of subscale not encountered among the copper alloys have been found Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation, i e , they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found The probable reasons for this difference in behavior will be discussed presently EXPERIMENTAL PROCEDURE Silver -The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99 993 per cent Ag)* and the purest avail-

Jan 1, 1942

By Jean L. Leroy

The Lead Smelting works of Metallurgie Hoboken S.A. are located on the banks of the river Scheldt a few miles South of Antwerp. Lead refining began at Hoboken in 1687, when it was restricted mainly to desilverizing lead bullion from Central America. Since then, various changes have been made to develop the works into a comprehensive and integrated custom smelter and refinery. Multiple hearth roasting furnaces, down-draft sinter machines and blast furnaces of standard design are used for the treatment of "complex" lead ores and secondary materials. A lead refinery based on the Harris process, with Parkes desilverizing followed by vacuum dezincing and Kroll Betterton debismuthizing was commissioned in 1967. Facilities for the recovery of precious metals, bismuth, antimony, arsenic and sulfuric acid are available. Special problems arise from the presence of large quantities of copper in the materials treated.

Jan 1, 1970

In many lines of engineering, much excellent standardization work had been done before the war but the war emphasized its importance and showed most clearly the need of cooperation to prevent the confusion caused by the promulgation of overlapping standards by independent bodies. The American Institute of Mining and Metallurgical Engineers, American Institute of Electrical Engineers, American Society of Civil Engineers, American Society of Mechanical Engineers, and American Society for Testing Materials, recognizing the value of what had been done, invited the Government Departments of War, Navy and Commerce to appoint representatives to act with them to continue this work; the body so formed is the American Engineering Standards Committee. It has required time to definitely formulate its objects and to arrange methods for accomplishing them that would be effective without interfering with the many organizations that have been doing such excellent work in this line. The American Engineering Standards Committee has just completed and adopted a revision of its Constitution, which has been sent to the Governing Boards of all the Departments and Societies represented on the Committee with a request for its ratification. The new Constitution changes the name to American Engineering Standards Association as more fittingly indicating the wide scope of the interests involved. The objects of the association are stated as follows: 1. To unify and simplify the methods. of arriving at engineering standards, to secure cooperation between various organizations and to prevent duplication of standardization work. 2. To promulgate rules for the development and adoption of standards, 3. To receive and pass upon recommendations for standards submitted as provided in the Rules of Procedure, but not to initiate, define, or develop the details of any particular standard. 4. To act as a means of intercommunication between organizations and individuals interested in the problems of standardization. 5. To give an international status to approved American engineering standards. 6. To cooperate with similar organizations in other countries and to promote international standardization.

Jan 7, 1919

By A. L. Labbe

SOON after the Cottrell treater was placed in operation in the Murray plant in 1918 to treat combined lead sinter and Wedge roaster smoke, it was noticed that the power flowing through the treater did not remain constant. This was indicated by the varying milliamperes and also by the total amount of power consumed by the rectifiers. At times, for then unknown reasons, the treater current fluctuated through a wide range of from 40 to 300 milliamperes. Fortunately, these variations in power did not affect the treater's overall recovery, as this installation consisted of three independent units in series, a feature which made the Murray Cottrell an outstanding installation over many years of operation. Water conditioning of the smoke as a means of improving recovery was already known, but was not adaptable to this installation for reasons of excessive corrosion, which had been the case with other treaters using water as a conditioner exclusively. Tests conducted on the smoke had proved conclusively that water vapor played no part in the fluctuation of power, and the same was true of the SO2 contents and dust burden of the smoke. Neither did temperature variations of from 150 to 400°F have any effect on the power. Finally it was noticed that the variation in power taken by the treater, and the efficiency of recovery, had some definite relation to the number of Wedge roasters operating, and particularly to the sulphur contents of the charge. This observation soon led to the discovery that free sulphuric acid was the conditioner for Murray smoke and that variations in acid contents of smoke accounted for fluctuations of treater power. Analysis of recovered dust revealed that only a few hundredths of a per cent free acid was necessary to maintain a very efficient recovery. Once this knowledge was available, the roaster charge was adjusted as to sulphur contents to produce the necessary acid conditioner. For a number of years this practice was followed, but with improvements in the field of flotation, excess pyrites were eliminated from the smelting picture, so with a change in metallurgical practice we were confronted with the problem of providing the deficiency in acid by some other means. The situation was aggravated and our problem of acid conditioning made more difficult by the increase in the lead contents of concentrates roasted resulting from better flotation methods. The first step towards introducing acid vapors into the smoke stream by accessory means was accomplished by boiling sulphuric acid in cast iron pots placed in an open fire box. Acid fumes evaporated from the pots together with the combustion gases from the fire box were discharged into the flue through a cast iron pipe. Capacity of the iron pots was quite limited because of the comparatively slow rate of evaporation and the use of lump coal as a fuel, which did not lend itself to practical temperature control. This method of firing resulted in frequent pot failures due to overheating. In spite of these incidental difficulties, encountered in any new venture, the pot evaporator demonstrated the practicability of fuming sufficient acid to make up the deficiency in that naturally evolved in the Wedge furnace operation. As time progressed, less and less high sulphur material was available for Wedge roasting, and the necessity for accessory acid conditioning reached a climax when the supply of this material was entirely eliminated. Since the cast iron pots could only evaporate a few hundred pounds of acid per day, and were costly to replace, the logical thought presented itself of spraying the acid in a heated chamber. This new type of acid evaporator was simpler and more economical to operate and had sufficient capacity to fume several thousand pounds per day. The attached fig. 1 presents the outstanding features of the new furnace. A is the vaporizing drum, which is heated by the combustion gases of coal stoker fire box, B. Acid is sprayed into the hot gas stream within the drum through a number of air-acid atomizers, C, and the acid vapor, together with combustion gases, is introduced into the smoke stream through two cast iron pipes extending to different points in the flue. The operation of this type of furnace requires control of temperature inside the drum to prevent overheating, which dissociates the acid vapor to SO, and eventually to SO2, with resulting loss of acid. The dissociation to SO, at elevated temperatures is comparatively high, and in some cases accounts for as much as 60 pct of the acid sprayed into the drum. To reduce the loss of acid, through dissociation, some Cottrell plants, where the rate of acid sprayed reaches at times 9 ppm, use two evaporating units. Fuming the acid into the smoke stream is only

Jan 1, 1951

By R. R. Webster, H. T. Clark

The side-blown converter has been investigated as a possible commercial process for the production of low nitrogen steel. During this work, two converters of 3-ton and 22-ton capacity were operated on a pilot plant basis for a total of 214 heats. The steel made in these converters was low in nitrogen and possessed good cold working properties. Some problems of converter operation remain to be solved. IN plants operating with a high iron capacity, sev-eral different refining methods are used in the conversion of the molten pig iron to steel. These include various ore practices in stationary and tilting open-hearths, the duplex process employing the Bessemer converter and open-hearth, and the Bessemer process. At J&L, a considerable part of the iron produced is handled by the Bessemer process, either alone or in conjunction with duplexing, and therefore an appreciable portion of the steelmaking research effort has centered about the method. This paper covers research work on the development of the side-blow converter for the commercial production of low nitrogen ingots and includes descriptions of the operation of a 3-ton and a 22-ton experimental converter at the Aliquippa Works. The refining of iron to produce steel requires the removal of a large portion of the carbon and silicon and the control of manganese, phosphorus and sulphur which are present in the iron in varying amounts. The first large-scale means of refining iron was the acid Bessemer process which was brought into use almost 100 yr ago. This method, using compressed air as the refining medium, accomplishes substantially complete removal of carbon, manganese and silicon. Phosphorus and sulphur are not affected but, by choice of an iron composition sufficiently low in these elements, a commercial product can be produced. Since the process will handle large tonnages rapidly, operates without external fuel and with a minimum of additional equipment, it quickly became the major tool in the early expansion of the steel industry. Later, the basic open-hearth process, by affording control of phosphorus and sulphur and by consuming the large quantities of steel scrap that were becoming available, forced the acid Bessemer process into a secondary position in the industry. During the past two decades the demand for steel to be used in cold forming and drawing operations has gradually increased. Bessemer steel, because of its work hardening and aging characteristics, is not as suitable for these applications as basic open-hearth steel, consequently the decline of the process was accelerated. More recently, because of changing economic conditions, this long range trend appears to have been arrested or perhaps reversed. Ingot production data for recent years furnishes only an incomplete picture of the importance of the converter in the American steel industry; open-hearth furnaces utilize large tonnages of blown metal for which no published statistics are available. Metallurgical Aspects The fundamental difference between Bessemer and open-hearth steels apparently lies not in the method of manufacture but, rather, in the differences in chemical composition of the two steels. It is further believed that the principal features distinguishing Bessemer from open-hearth steel are the higher nitrogen and phosphorus contents of the former. Evidence supporting this position is supplied by tests on laboratory induction furnace heats that were made to contain varying amounts of phosphorus and nitrogen but were otherwise similar to normal low carbon silicon-killed steels. Fig. 1, 2 and 3, summarizing the test results, are taken from G. H. Enzian's paper titled, "Some Effects of Phosphorus and Nitrogen on the Properties of Low Carbon Steels."' Fig. l indicates that phosphorus has a marked effect on the cold work embrittlement of steel as shown by the work brittleness test of Graham and Work.' In the low nitrogen steels, which as a group have the better cold working properties, the effect of phosphorus variations is the more pronounced.

Jan 1, 1951

By G. K. Manning, A. R. Elsea, C. R. Simcoe

Boron increases the hardenability of hypoeutectoid steels by decreasing the nucleation rate of ferrite and bainite. It is postulated that concentrations of lattice imperfections, such as exist at the grain boundaries, furnish the necessary energy for nucleus formation. Boron, because of its atomic diameter, will concentrate at lattice imperfections where sites of suitable size are present. Boron will decrease the energy of these local areas by occupying these sites. This mechanism accounts for the large increase in hardenability observed with small amounts of boron. The loss of the boron hardenability effect and the boron precipitate formation are explained on the basis of increased concentration of boron at the grain boundaries either with increasing boron content of the material or with increasing temperature. COMMON alloying elements affect both the nucleation and growth rates of the austenite decomposition reactions.' This effect is largely a result of the slow diffusion rates of these elements. Although a small addition of boron markedly increases the hardenability of steel, the diffusion rate of boron, which is of the same order of magnitude as that of carbon, can hardly account for this effect. An addition of boron in the range of 0.001 to 0.003 pct is about as effective as an addition of 0.30 pct Mo, 0.40 pct Cr, or 1.25 pct Ni in increasing the hardenability of a 0.40 pct C steel;' however, increasing the carbon content of the steel decreases the effectiveness of the boron addition."' The difficulty in understanding why so small an addition of boron can replace much larger quantities of the more strategic alloys, together with the erratic behavior sometimes encountered in boron-treated steels, has interfered with their general acceptance by industry. In the belief that an understanding of the mechanism by which boron increases the hardenability of steel should lead to a more general acceptance of boron-treated steels, a research investigation to determine this mechanism was undertaken at Battelle Memorial Institute under sponsorship of Wright Air Development Center. Experimental Work In order to study the effect of boron on the transformation of austenite to ferrite and bainite, a group of steels was made with a basic composition similar to that of the SAE 8600 series. This base composition was chosen because it has sufficient hardenability to permit accurate measurement of the times required for transformation to start at various temperatures. The chemical analyses of the steels used in the first part of this investigation are listed in Table I. These steels were made as 200 lb heats in an induction furnace. The furnace charge was Armco ingot iron with the alloying elements added as ferroalloys. After the alloy additions were made, the heat was deoxidized with 0.125 pct Al. A 100 lb ingot was cast and an addition of 0.003 pct B, as ferroboron, was made to the metal remaining in the furnace. This metal was cast into a second 100 lb ingot. The ingots were forged to 11/4 in. diam bar stock from which end-quench hardenability specimens were obtained. Part of this material was further reduced by hot rolling to lx¼ in. bar stock from which specimens were obtained for isothermal transformation studies. Studies of Nucleation and Growth: End-quench hardenability tests were performed on these steels, using an austenitizing temperature of 1600°F. The hardenability curves, shown in Fig. 1, indicate that boron treatment resulted in considerable increase in hardenability of the steels. Any such change in hardenability must result from a change in the transformation rate of the austenite, and these rate changes can be established readily by isothermal transformation studies. Isothermal transformation studies were conducted on these steels as follows: specimens were austeni-tized at 1600°F for 15 min, transferred to a lead bath operating at a constant subcritical or intercritical temperature, held for various lengths of time, and water quenched. The specimens were sectioned for metallographic examination to determine the amount and the type of transformation products present. In order to determine the effect of boron on the formation rate of ferrite, isothermal transformation tests were made on the 0.20 pct C steel in both the boron-treated and boron-free condition at an intercritical temperature of 1375°F where ferrite is the only decomposition product of this low carbon austenite. The results of these tests are shown in Fig. 2, where the percentage of ferrite formed is plotted as a function of time at temperature. It is apparent that boron markedly decreased the transformation rate of austenite to ferrite at this temperature.

Jan 1, 1956

By G. L. F. Powell

g samples of Cu-20 wt pct Ag alloy have been mdercooled to a maximum of 197°C by melting under a slag of commercial soda-lime glass in a vitreous silica crucible. No grain refinement of the primary copper was observed in samples undercooled to the maximum of 197°C. When the samples contained a small amount of oxygen, the copper dendrites were partially recrystallized at undercoolings greater than 97°C. In previous papers'-3 reporting the grain structure of undercooled silver and copper, it was observed that grain refinement was dependent on both undercooling and oxygen content. Grain refinement occurred in undercooled silver when the degree of undercooling exceeded the range 153" to 175"C, while in Ag-0 alloys (0.12 wt pct) fine equiaxed grains were exhibited when undercooling was greater than 50°C. Similarly, copper samples undercooled as much as 208°C displayed fan-shaped growth from a single nucleation site, while the grain structure of Cu-O alloys (0.08 wt pct) was fine and equiaxed at undercoolings larger than 150°C. Thus the presence of oxygen greatly reduced the undercooling at which grain refinement occurred. It was also observed that the change in grain size resulted from recrystallization and was not due to an enhanced nucleation rate in the liquid-solid transformation. It is possible that the influence of oxygen on recrystallization is due primarily to its presence as a solute element. walker4,' reported that, although a grain size change did not occur in pure nickel until the undercooling exceeded 150°C, small grains were observed in samples of Ni-Cu alloy solidified at small and large degrees of undercooling. Jackson et al.6 suggested that the fine grained structure of the Ni-Cu alloy resulted from the melting off of dendrite arms during recalescence. This remelting process may occur in alloys as a result of segregation during freezing which causes a variation in liquidus temperature from point to point within a dendrite. It was therefore decided to undercool copper with a metallic alloying element to ascertain whether the presence of a metallic solute would have a similar effect to oxygen in inducing grain refinement. A Cu-Ag alloy was chosen, since both metals had been shown to behave similarly on undercooling. The alloy Cu-20 wt pct Ag was selected since the eutectic constituent outlines the initial growth form of the primary copper, so that the as-frozen grain structure is not obscured if subsequent recrystallization occurs. This paper describes the results of undercooling experiments carried out with Cu-20 pct Ag samples undercooled to a maximum of 197°C and the effect of oxygen content on the grain structure of the undercooled samples. EXPERIMENTAL Melting was carried out in a small cylindrical resistance furnace using "fine" silver granulate and oxygen-free high conductivity copper. The procedure adopted was to melt the required quantity of silver in air in a clean vitreous silica crucible for approximately 15 min, freeze, and add granulated commercial soda-lime glass to form a complete surface slag cover, after which the sample was melted and frozen several times to reduce the oxygen content. The glass slag cover was approximately 3 in. thick. Pieces of copper (=50 g) were added to the crucible until the required quantity to make 350-g samples of alloy had been charged. Each piece was added quickly to the crucible which was held at a temperature slightly above the melting point of silver. The piece was quickly pushed beneath the glass to minimize oxidation and any oxide coating usually decomposed before the piece had settled down into the silver. After the full quantity of copper had been added, the melt was stirred with a silica rod to hasten homogenization and a Pt/Pt 13 pct Rh thermocouple enclosed in a vitreous silica sheath inserted for temperature measurement. Heating and cooling curves were recorded on a potentiometric chart recorder fitted with a zero suppression unit. The milli-voltage range of the recorder was adjusted so that temperatures could be read to 1°C. Heating and cooling curves were taken every hour until three consecutive readings gave the same solidus-liquidus range, consistent with the solidus-liquidus range for this alloy composition by reference to Hansen and Anderko.7 Metallographic examination of samples frozen at this stage, failed to show any variation in composition from bottom to top of the ingot. Consequently, it was considered that the melt was homogeneous at this stage and undercooling experiments were then car-

Jan 1, 1970

By H. W. Schadler

The superplastic behavior of low carbon and manganese bearing steels has been evaluated. The results of elevated-temperature stress-strain rate and elongation tests are reported which indicate that high strain rate sensitivity (>0.5) and adequate elongations are achievable in ultrafine-grained steels 1 to 2 p, but at strain rates which are not commercially attractive. It has been demonstrated that the fine grain size is retained after long times and high strains if the temperature is kept within the range of the two-phase (a + ?) field. INTEREST in superplasticity has been stimulated by the desire to: 1) understand the origin of, and mechanisms responsible for, the large uniform elongations observed, and 2) exploit this property for commercial advantage in metal forming operations. Although the Zn-22 wt pct Al alloy presently being studied as a model material1-5 may find application in sheet forming and extrusion, the potential of super-plasticity should best be realized in large tonnage materials, such as steel and aluminum alloys. The degree of superplasticity in low-carbon and manganese-bearing steels has been evaluated. The results of elevated-temperature stress-strain rate and elongation tests on ultrafine grain size material are reported. Avery and Backofen6 and Hart7 have shown that geometrically stable flow leading to extensive uniform elongation in the tension test is associated with high values of the strain rate sensitivity, m, defined: Lozinsky had reported that titanium and zirconium experience permanent deformation if subjected to a constant load and cyclic heating through the temperature range of the phase transformation. Although strain rate sensitivities in excess of about 0.2 had not been reported previously for steel, permanent deformation had been observed11-13 in a wide variety of steels subjected to a constant load and cyclic heating through the temperature range of the a-? phase transformation. Thus by analogy, steel could be expected to exhibit high strain rate sensitivity but only in the a + ? condition. High strain rate sensitivity has been observed at 650°C (a + Fe3C), but not reported as such, by Bailey, Dickenson, and pearson14 in 1931 at a strain rate of about 10-9 per min. It then remained to determine whether high tensile elongations would be observed in a rate-controlled test at constant temperature and at what strain rate strain rate sensitivity values greater than 0.5 would be observed. Since previous experience8 had indicated the importance of fine grain size to realizing high m at reasonable strain rates, it was first necessary to produce an ultrafine grain size and then keep the grains from growing during the test. The results of this investigation show that fine grain size can be readily produced16 and maintained by restricting the temperature of testing to below the ? transus. Further, superplasticity (high m and large uniform elongation) is observed. However, the strain rate range is only marginally useful for commercial forming operations with the finest grain size produced. MATERIAL The material investigated initially was a 1.9 wt pct Mn, 0.42 wt pct C, hot-rolled bar previously used by Low and Turka1015 and available in the laboratory. The 0.500-in. round was cold-rolled to a 0.090-in. flat, annealed for 4 hr at 850°C in argon, air-cooled, and cold-finished to 0.050 in. Subsequently, four additional steels of the compositions given in Table I were investigated to explore the effects of manganese, carbon, and test temperature on the observed stress-strain rate behavior. These steels were melted under argon, cast to 0.75 by 2 by 5 in. slabs, hot-rolled at 850°C, surface-finished to 0.13 in., and cold-finished to 0.050 in. Sheet tensile specimens 0.200 in. x thickness with 1- or 2-in. gage length were cut parallel to the rolling direction. Table I also includes the nominal transformation temperatures for the AISI 1340 and the four experimental steels. EXPERIMENTAL PROCEDURE Production of Fine Grain Size. Ultrafine grain size (1 to 5 p) was considered essential for this studv. Grange16 has described two techniques for producing

Jan 1, 1969

IN accordance with a programme arranged by a committee of the Institute, consisting of Mr. William P. Shinn, of St. Louis, chairman, and Mr. Joseph D. Weeks, of Pittsburgh, secretary, the member's of the Institute, with their ladies and invited guests, assembled in Chicago on Sunday morning, August 22d. A special train, provided by the Chicago and Northwestern Railway,. left Chicago on Monday morning at 7.50 o'clock, and conveyed the party to Marquette, arriving at 9 o'clock P.M. Here the steamer Northern Queen, which had been chartered by the committee for the accommodation of the Institute, was in waiting, and the members and ladies at once took up their quarters on the boat. EXCURSIONS IN THE MARQUETTE IRON REGION. Local Committee. EXECUTIVE. -J. C. Morse, chairman; C. Y. Osburn, secretary ; D. F. Wadsworth, treasurer; C. H. Hall, H. Merry. RECEPTION.-S. P. Ely, J. P. Pendill, E. Breitung, W. F. Swift, A. P. Swineford, J. C. Fowle, C. G. Griffey. TRANSPORTATION.-Samuel Schoch, D. Morgan, D. H.. Merritt, J. Pickands. FINANCE.-Peter White, A. W. Maitland, W D. Rees, E. R. Hall. EXCURSIONS.-W. E. Dickinson, H. A. Burt, A.. Kidder, C. E. Wright. REFRESHMENTS.-J. Q. Adams, H. H. Stafford, Joseph Kirkpatrick, D. H. Bacon. On Tuesday the iron mines in the vicinity of Negaunee and Ishpeming were visited, transportation being provided by special trains on the Marquette, Houghton and Ontonagon Railroad. In the morning the McComber, South Jackson, and Jackson mines were inspected, and in the afternoon the Cleveland, New York, Lake Superior, and Barnum mines. Dinner was provided at Negaunee, and gracefully served by, the ladies of the town. In the evening the first session of the Institute was held in the saloon of the steamer. The President, William P. Shinn, of St. Louis, congratulated the Institute on the happy consummation of the wishes of its members to have a meeting on Lake Superior. After tedious and baffling negotiations arrangements had been com-

Jan 1, 1881

By J. W. Cunningham, W. A. Tiller, D. H. Lane

The effect of ultrasonic vibrations on ingot solidification has been considered both theoretically and experimentally. The theoretical section elucidates the mechanisms by which the ultrasonic vibrations might refine the ingot structure. The experimental section describes a very efficient means of introducing the ultrasonic vibrations to the freezing interface. The application of this technique to the consumable-electrode arc melting process shows that the columnar mode of freezing may be effectively suppressed yielding an ingot structure consisting predominantly of equiaxed grains. The results support the contention that the ultrasonic vibrations increase the nucleation frequency in the layer of liquid adjacent to the freezing interface. CERTAIN structural characteristics of as-cast ingots are undesirable since they create considerable difficulty for subsequent processing and often produce defects in the finished product. These structural defects are illustrated in Fig. 1(a), and are: 1) planes of weakness where columnar grains growing from the different mold faces meet, 2) strength anisotropy due to the preferred orientation of the columnar grains and 3) inhomogeneity due to segregation at dendrite boundaries within the columnar grains and at the columnar grain boundaries. The type of ingot structure that eliminates 1) and 2) and diminishes 3) is the fine-grained equiaxed structure illustrated in Fig. 1(c). Many attempts have been made to produce the desirable ingot structure illustrated in Fig. 1(c) by inoculating, casting with varying superheats, vibrating or stirring, or by irradiation with ultrasonic vibrations. These attempts have met with various degrees of success, the ingots generally having the structure illustrated in Fig. 1(b). All four methods have been the subject of numerous investigations,1"4 the latter producing the most erratic behavior and inconsistent success. The method of ultrasonic irradiation during ingot solidification has shown considerable promise on small-scale ingots (diam 2 in.) but has not yet been successfully adapted to large-scale operation. The present paper considers the application of ultrasonic radiation to ingot solidification both theoretically and experimentally. The purpose of the paper is to elucidate the mechanism by which ultrasonic energy refines the ingot structure and to describe a method for producing the desirable ingot structure in both laboratory scale experiments and in ingots of commercial size. THEORY Conventional Casting—Before discussing the possible effects of ultrasonic radiation upon ingot structure let us first briefly review the reasons for the breakdown of columnar crystallization to equiaxed crystallization during ingot solidification. The following is a slightly oversimplified description. In the conventional method of casting, the alloy having a certain degree of superheat, T, is poured to fill a cold mold which is at room temperature, Tc,. Due to conduction of heat through the mold wall the outer rim of liquid metal cools rapidly to the liquidus temperature and begins to supercool. At some degree of supercooling, nuclei of solid form at random in this supercooled layer at the mold surface. The grains in this chill layer begin to grow inwards producing a solute build-up, thus lowering the freezing temperature at the interface as illustrated in Fig. 2. As growth proceeds, the temperature gradient in the solid conducts away not only the latent heat of fusion evolved during growth but it also conducts away some of the superheat of the melt so that the temperature

Jan 1, 1961

By Wm. A. Haven

ON the northern part of the globe, almost since the earliest days of mankind's history. ironmaking has been practiced in one form or another. Some investigators question the generally accepted belief that copper and bronze were in earlier general use than iron, explaining the greater age and abundance of copper relics by their greater resistance to natural oxidation. However, the occurrence of copper in its natural state and its greater ease of reduction from the simpler copper minerals is a strong argument that the making and use of copper came first. Nevertheless, good evidence exists that ironmaking was practiced in ancient India and China, as well as in ancient European countries. Some interesting vestiges of those early operations still survive and have a place, in the background at least, of a discussion of modern blast-furnace practice.

Jan 1, 1940

By E. I. Salkovitz, F. W. von Batchelder

DURING the last few years several papers1-' have been published in which internal friction measurements have been used to determine the quantity of carbon or nitrogen dissolved in a iron. This method is based on the fact that, in pure Fe-N and Fe-C alloys, nitrogen and carbon cause peaks in the internal friction vs. temperature curve; at a frequency of 1 cycle per sec (cps) these peaks appear at $-200 and +360C, respectively, and if internal friction is expressed as Q-1, which is equal to times the logarithmic decrement, this figure will, by coincidence, give the weight percentage of nitrogen or carbon in solid solution.' In most of the studies published, very pure iron (Puron) was used. In one case the influence of manganese on the behavior of nitrogen in a iron was mentioned.4 It would be of great value, especially for the study of aging and related phenomena, if this method could be applied to commercial mild steel with norrnal percentages of manganese, phosphorus, sulphur, etc. As a rule, in such steels carbon and nitrogen are present together, and the amounts of these elements in solid solution should preferably be determined separately. The fact that their internal friction peaks appear at different temperatures (+36° and + 20°C in pure iron) seems promising for such a selective determination. It is necessary, however, that the peaks are narrow enough not to interfere with one another, and further, that there is no effect from carbon on the behavior of nitrogen in stress induced diffusion, and vice versa. According to Fast,' however, in the presence of manganese the nitrogen peak gets wider and appears at a higher temperature nearer the carbon peak, and thus the prospects for selective determination are reduced. (The carbon peak was not affected by the presence of manganese.) But even if fully quantitative de- terminations of the two elements are not attained, some relative figures on the sum of them and an indication of which one is the predominant one, would be of value. Some results from experiments along these lines will be reported here. An internal friction measuring device was assembled mainly following a description by KG." The measurements were also carried out as reported in that paper. Table I gives the chemical compositions of the four different materials used in this investigation. All materials were drawn to wires with diameter about 0.8 mm, and the analyses refer to these final shapes. Determination of Nitrogen Peak Wires from steels A, B, and C were decarburized in wet hydrogen (about 30 pct H2O) at 700°C until no carbon or nitrogen could be found by chemical analysis. No peak was then found in the internal friction. The wires were further annealed at 580°C for 16 hr in hydrogen bubbled through a solution of 6.8 pct NH3 in distilled water. Chemical analyses gave 0.04 pct N in A and C, and 0.06 pct in B. After annealing at 580°C for 15 min in a lead bath and water quenching, the internal friction was immediately measured. The resulting curves are shown in Fig. 1. At these high values of the internal friction the accuracy is comparatively poor; at Q-1 - 0.030 it is estimated to be 0.002. In order to make possible a calculation of the activation energy for diffusion of nitrogen, measurements were made at two different frequencies. Steel A shows rather broad peaks, and their temperatures can hardly be expected to be very accurate. Steels B and especially C are better in this respect. The finding of Fast' that manganese broadens the nitrogen peak is con-

Jan 1, 1953