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By R. R. McNaughton

The Consolidated Mining and Smelting Company of Canada, Ltd. at Trail, B. C., inaugurated a comprehensive program of investigation about 15 years ago to develop the most economical process of recovering the metal in the large accumulated stock of by-products of the lead smelter and the zinc plant. Two principal methods of recovery were followed to a successful conclusion—an electrothermic process to treat zinc-plant residues and cold slag and the fuming of hot slag from the lead blast furnaces. The latter was selected because it showed a saving over the former in its ability to handle hot blast-furnace slag, thus obviating the necessity of granulating, handling and eventually remelting the same slag for the electrothermic process. The design of a fuming plant was commenced in 1928, and construction, which was started immediately, was completed in July 1030. Operating intermittently for a general tuning up, the plant was officially blown in for regular operation in August. During this month the vagaries of a slag-fuming plant were studied and an operating crew was trained. A history of slag fuming at Trail and the development of plant design is given in a paper by G. E. Murray in the Transactions of the Canadian Institute of Mining and Metallurgy for 1933. Fuming Plant The fuming plant at Trail (Fig. 1) is a separate unit although of necessity interlocked closely with the lead smelter. The plant consists essentially of a fuming furnace with its accessories, a waste-heat boiler followed by an economizer, and a suction-type baghouse. The plant was built as the first of two 400-ton units with the intention of adding the second unit within a year, so that flues, fans and buildings were built to handle double the original load. Furnace.—The furnace as originally built (Fig. 2) was of water-jacket construction, 10 ft. wide, 20 ft. long and 6 to 10 ft. high. The roof height was made variable to check experimental work, which had indicated that this dimension affected the rate of reduction. Coal and air were supplied

Jan 1, 1937

By Nathan C. Rockwood

LIME is a very general term applied to products of limestone, in popular treatises often incorrectly, including ground or pulverized limestone used in agriculture. When used without qualifying adjective, the term usually means burned or calcined limestone, or quicklime, or calcia. The corresponding calcined product of magnesite is magnesia. If the calcined rock is relatively pure calcium carbonate, the resulting lime is a "high-calcium" lime; if the rock is dolomite, or a combination of calcium and magnesium carbonates, the lime is a "dolomitic" or a "high- magnesium" lime. There are various grades in between, depending on the percentage of magnesium carbonate and other ingredients in the raw rock. For some industrial purposes only high-calcium limes are suitable; in other processing-as, for example, neutralizing acid wastes -the relative percentages of magnesium and calcium carbonates in the raw material are not important. Limestone is burned (roasted or calcined) in furnaces known as lime kilns by direct exposure to the hot gases and flames. When heated to incandescence, the carbon dioxide content of the rock is expelled, leaving calcium and magnesium oxides, according to the formula usually written: [ ] This thermal reaction is reversible, which requires that the lime be withdrawn from the "calcining zone" of the kiln about as fast as made. Pure calcium carbonate would lose 44 pct of its weight in the calcining process; dolomite, 48 pct. Generally, the lime will retain the approximate size and shape of the piece of rock from which it is made but some few limestones tend to break down into granules or dust. Hence lime (quicklime) comes from the kilns in lumps or granules and normally is packed in water- tight containers in these forms, or is pulverized after calcination.

Jan 1, 1949

By A. F. Giamei, E. J. Freise

A discussion of the various factors affecting the accuracy of volume fraction determination by the direct comparison X-ray diffraction method is presented. To minimize errors introduced by nonrandomization effects such as preferred orientation and large grain size, as well as errors introduced by statistical effects, an iterative mathematical analysis is introduced. This analysis is applied to all observable diffractio~ spectra from a given specimen by means of computer techniques and is statistically superior to the standard direct comparison technique which utilizes only one or tm sets of intensity spectra. The computer program also presents a graphical interpretation of- the results which enables the investigator to visualize and readily assess the scatter in volume fraction estimates caused by deviations from randomness. Finally, the iterative analysis is applied to experimental data collected from a series of plain carbon steels in both the as-received and spheroidized conditions to determine the volume fraction of cemen-tite present in each case. The results show markedly good agreement with chemical analyses for all spheroidized specimens. In theory, quantitative X-ray diffraction is a power-ful analytical technique for precise determination of the volume fractions of various phases present in a multiphase poly crystalline aggregate. There are two generally used methods; both utilize the fact that the intensity of a diffraction line of a particular phase is a function of volume fraction of that phase present in the aggregate. The more common method is the so-called internal standard technique where a known amount of standard substance is mixed with the aggregate containing the unknown. The resulting ratio of the intensity of a particular diffraction line of the unknown to the intensity of a diffraction line from the standard is used to find the weight fraction of unknown material by reference to the intensity data obtained from a previously prepared set of standards containing the same amount of standard material. The details of this technique are outlined in standard works on X-ray diffraction.' The disadvantages of the technique are that it requires the use of powder specimens and that the powder mixture must be homogeneous near the surface to the maximum effective beam depth. The alternative technique is the direct comparison method in which the ratio of the intensity of a diffraction line of a phase in the aggregate to the intensity of a second-phase diffraction line yields the ratio of the volume fractions of each phase present. This method has been applied most extensively to the determination of the percentage of retained austenite in martensitic steels and to determining the amounts of hcp and fcc allotropic modifications in pure cobalt5 and the amounts of hexagonal and rhombohedra1 modifications in graphite.8 This method is applicable to bulk as well as powder aggregates and is the technique which will be considered in the following text. It is the purpose of the present communication to show that by combining the results of X-ray diffrac-tometry with the use of high-speed digital computers the results of the direct comparison quantitative X-ray analysis technique can be optimized by using all of the data available on a diffraction pattern. THEORETICAL DISCUSSION In optimizing any quantitative X-ray diffraction experiment, the problem of accuracy vs time to collect and analyze the experimental data arises. For any method to be practical, it is required that both experimental and analytical procedures are reasonably short. In most of the previous work performed by the direct comparison method, intensity data from only one or two sets of peaks were used to calculate the volume fraction of phases present in the aggregate. Consequently, rather long-time experimental measurements are required to assure that the intensity data are sufficiently accurate to justify the use of one or two sets of data. By using computer techniques to analyze the experimental data it becomes feasible to use all of the available data on a diffraction pattern. By so doing, the time spent in measuring any one diffraction maxima can be appreciably reduced. Although this results in poor counting statistics for any one maxima, the number of data points available for analysis is greatly increased. Based on the above discussion, it will be assumed that a continuous scanning counter-diffractometer technique will be used to collect intensity data from a two-phase mixture. The integrated intensity of the ith diffraction line from the a phase in the aggregate is given by:'" where is the volume fraction of the a phase, The various quantities in Eq. [la] are angular independent while those in [lb] depend on the hkl spectrum of a particular phase. The meaning of the individual quantities in Eqs. [la] and [lb] are given in Appendix 1. It is convenient at this point to outline briefly the factors which will affect the measured intensity of any one hkl spectrum. a) Extinction effects arise from two independent experimental conditions. Primary extinction arises from a high degree of crystal perfection and results in spectra having lower intensity than predicted by Eq. [I]. Any treatment, such as powdering, which reduces

Jan 1, 1968

By Frederick T. Fischer

INTRODUCTION Post-Lower Ordovician karstification on a continental scale produced a wide-spread paleoaquifer in the upper portion of the Knox Group of the Southeastern United States. The presence of economic zinc deposits in the Knox of Tennessee is considered to be a con- sequence of this paleoaquifer(1). During The New Jersey Zinc Company's initial exploration of the middle Tennessee region the known artesian nature of modern Knox water and its potentially adverse effect upon mining activities was a matter of concern. This concern intensified as a mining situation appeared imminent and a program of hydrologic investigation was begun in early 1969 and continued through August 1972. The preliminary findings of this work were reported at the AIME World Symposium on Mining and Metallurgy of Lead & Zinc in 1970(2). This paper presents additional data acquired during subsequent stages of the program and relates the hydrologic relationships to the overall geologic framework of the area. PHYSICAL GEOGRAPHY The Elmwood mine is 85km east of Nashville and 8km southeast of Carthage in Smith County, Tennessee (Figure 1). Its physiographic location is in the Central Basin of Tennessee, a basin resulting from erosional breaching across the Nashville Dome of the Mississippian strata which now form the bordering Highland Rims. Both the Central Basin and Highland Rims are divisions of the Interior Low- lands Province. Outcropping rock units of the Central Basin are predominantly Middle Ordovician limestones with scattered high hilltops capped by Devonian and Mississippian strata. One outlier

Jan 1, 1977

By C. E. Sims, G. A. Lillieqvist

The following presentation is more a summation of observations made and conclusions drawn over a period of three to four years than a report of experiments made with a definite objective. Tests were made, of course, to verify hypotheses, but the large mass of data was collected incidental to other work. Lack of space forbids the presentation of more than a few of those data. On the other hand, it is unfortunate that some of the most illustrative examples are not available. The work is admittedly incomplete but is presented in the hope that it will stimulate further work along a similar line. The answers to many of the questions left unanswered by this paper will be found only after long and painstaking study, such as is scarcely possible in a commercial laboratory where problems of immediate importance consume most of the time. It is also hoped that this study will in some measure throw light on some of the dark spots of steelmaking, and help to clarify some of the annoyingly vague references to "good practice." Only cast steel was studied and the conclusions apply to cast steel, but it is the authors' opinion that the quality of rolled or forged steel is largely dependent on the quality of the ingot, which is a casting. Although this discussion deals almost entirely with inclusions, it is important that the reader understand that only those natural inclusions which owe their origin to the solubility of certain materials in steel and to the chemical reactions of steelmaking are considered. Accidental inclusions, such as entrapped particles of slag, nozzle, runner, or mold arc outside its province and are not considered. Such accidental inclusions are always dangerous and should be carefully avoided. Relation between Ductility and Nonmetallic Inclusions In September, 1928, an acid electric furnace was put into operation at the Indiana Harbor plant of the American Steel Foundries. Following the usual practice, aluminum additions were made in order to obtain sound castings. Immediately the problem of low ductility arose. Previous to that time, only open-hearth steel was produced, and, aluminum being used rarely in that steel, there had been practically no trouble with low ductility in the lower carbon range.

Jan 1, 1932

By Nicholas J. Grant, William H. Ferguson, Bill C. Giessen

Ta-lr alloys have been examined over the complete range of compositions using metallographic and X-ray techniques. The terminal solid-solubility limits, solidus temperatures, and intermediate phases were determined. There are four inter-mediate phases: o, tetragonal, analogous to a (Fe-Cr); 0,. orthorhombic; az, tetragonal; and a TaZr,, cubic, AuCu, structure. Of these, o and a, melt peritecticaLly, a, decomposes peritectoidally, and a TaIrs has a congruent melting point. Three peri-tectic and one eutectic reactions occur. 1 HE Ta-Ir phase diagram has not been treated in the literature. Intermetallic phases and terminal solid solubilities have been described and estimated.'-4 The previous findings have been confirmed in this work. A complete diagram with additional phases and solidus curves is presented. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by the National Research Corp., Cambridge, Mass., and iridium powder of 99.9 pct purity, supplied by the Bishop Co., Malvern, Pa. Both powders were -200 mesh. Table I lists the analyses as given by the suppliers. A standard procedure was employed in making the alloy buttons, which was described in detail in Refs. 5 and 6, and which included repeated arc-melting of powder compacts and determination of the composition by the weight-balance method. This is especially justifiable due to the similar vapor pressures of tantalum and iridium. In the critical parts of the diagram, a spacing of 1/2 at. pct was used, based on premelted master alloy material. The observed structures and X-ray spectra were consistent with the composition sequence of the alloys. Table II lists the final alloy atomic percentages with the calculated percent error of composition. Cross sections representative in grain size and composition were selected for the study, as described in Ref. 5. Based on prior experience, no contamination from the tungsten electrode was considered. Temperature measurements were obtained using a Leeds and Northrup optical pyrometer and have been described extensively in Refs. 5 and 6. All heat treatments were made in the high-vacuum tantalum tube furnace mentioned in Ref. 5. Samples annealed in tantalum containers cooled from 1800" to 1000"~ in 5 sec; those annealed in ceramic crucibles cooled over the same range in 15 to 30 sec. The thermal treatments are listed in Table 111. All specimens were homogenized at 1735°C for 24 hr. Tantalum-rich compositions were treated in tantalum buckets. Iridium-rich compositions were annealed in tantalum buckets below the eutectic temperature of 1950°C; up to 2200°C, tungsten-lined tantalum baskets were used; and above 2200°C thoria crucibles were used. It was found that refractory oxides (in early stages of the investigation alumina crucibles were used up to 1800°C and thoria crucibles were used to 2400"~) give off minute amounts of oxygen and thereby influence the microstructure considerably, or react directly with the alloys.

Jan 1, 1963

By Taylor Lyman, E. P. Klier

The structures formed when austenite is quenched to subcritical temperatures and allowed to transform isothermally have been the subject of intensive study since the work of Davcnport and Bain.' Isothermal transformation diagrams summarizing the results of many of these studies have become widely familiar to metallurgists. Of particular interest to metallographers are the dark-etchingl acicular products of transformation formed by isothermal reaction below the temperature of maximum velocity of the austenite to pearlite reaction. These products, the bainite structures, can he formed in a wide variety of steels. However, the constitution of bainite is not well understood and divergent views have been expressed as to its mode of formation. In this investigation a combination of dilatometric, microscopic and X-ray methods has been brought to bear upon the problem in the hope of some elucidation of the bainite reaction as it occurs in hypo-eutectoid steels. Mechanism OF Bainite Formation Davenport and Bainl considered the mechanism of bainite formation to consist of two steps—an allotropic transformation followed by precipitation of carbide. The separation in time of the two processes was considered to be very slight in the upper temperature range and very marked at temperatures just above the martensite range. This concept has been restated by Vilella, Guellich and Bain2 in the form of a definition of the acicular mode of transformation as: The successive, abrupt formation of flat plates of supersaturated ferrite along certain crystallographic planes of the austenite grains; this supersaturated ferrite begins at once to reject carbide palticles, (not lamellae), at a rate depending upon temperature In effect, this is the acicular mode of transformation, even though the temperature be such as to limit the actual life of the quasi-martensite to millionths of a second. The investigation of isothermal decomposition of austenite in certain alloy steels (notably those containing chromium or molybdenum) has revealed that there may be a range of temperatures between the pearlite and bainite reactions in which the austenite decomposes at a relatively low rate.3-6 Further, it is characteristic that in the second region of fast reaction the decomposition of the austenite is incomplete by one reaction but goes to completion by a second reaction. These observations led Wever7 to a description of the bainite reaction as follows: I. The reaction takes place by initial precipi. tation of a martensitic intermediate structure. 2. In the upper temperature range this structure readily decomposes into ferrite and cementite. In the lower range carbon separates in an unknown form. 3. In the upper temperature range the precipitated carbide nucleates the precipitation

Jan 1, 1944

By E. P. Klier, Taylor Lyman

The structures formed when austenite is quenched to subcritical temperatures and allowed to transform isothermally have been the subject of intensive study since the work of Davcnport and Bain.' Isothermal transformation diagrams summarizing the results of many of these studies have become widely familiar to metallurgists. Of particular interest to metallographers are the dark-etchingl acicular products of transformation formed by isothermal reaction below the temperature of maximum velocity of the austenite to pearlite reaction. These products, the bainite structures, can he formed in a wide variety of steels. However, the constitution of bainite is not well understood and divergent views have been expressed as to its mode of formation. In this investigation a combination of dilatometric, microscopic and X-ray methods has been brought to bear upon the problem in the hope of some elucidation of the bainite reaction as it occurs in hypo-eutectoid steels. Mechanism OF Bainite Formation Davenport and Bainl considered the mechanism of bainite formation to consist of two steps—an allotropic transformation followed by precipitation of carbide. The separation in time of the two processes was considered to be very slight in the upper temperature range and very marked at temperatures just above the martensite range. This concept has been restated by Vilella, Guellich and Bain2 in the form of a definition of the acicular mode of transformation as: The successive, abrupt formation of flat plates of supersaturated ferrite along certain crystallographic planes of the austenite grains; this supersaturated ferrite begins at once to reject carbide palticles, (not lamellae), at a rate depending upon temperature In effect, this is the acicular mode of transformation, even though the temperature be such as to limit the actual life of the quasi-martensite to millionths of a second. The investigation of isothermal decomposition of austenite in certain alloy steels (notably those containing chromium or molybdenum) has revealed that there may be a range of temperatures between the pearlite and bainite reactions in which the austenite decomposes at a relatively low rate.3-6 Further, it is characteristic that in the second region of fast reaction the decomposition of the austenite is incomplete by one reaction but goes to completion by a second reaction. These observations led Wever7 to a description of the bainite reaction as follows: I. The reaction takes place by initial precipi. tation of a martensitic intermediate structure. 2. In the upper temperature range this structure readily decomposes into ferrite and cementite. In the lower range carbon separates in an unknown form. 3. In the upper temperature range the precipitated carbide nucleates the precipitation

Jan 1, 1944

By Michael Perch, Charles C. Russell

Nearly 75 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank' standardized by the American Society for Testing Materials. Although this method of classification has been an American stand¬ard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1944

By W. A. Ver Wiebe

The year 1940 was singularly unmarked by sensational developments in Kansas. Routine operations were carried on in a systematic, orderly fashion and the efforts of oil producers were concentrated on extending known fields. In Kansas an arbitrary yardstick for wildcats has been set up. A well drilled mile or more from a known pool or well is now considered a wildcat. A "rank wildcat" is one that is drilled at least 2 miles from any known producer. During 1940, rank wildcats resulted in the completion of 116 test wells, among which 16 were successful in finding new oil pools and the remaining I00 were dry holes. The ratio of successful wells to dry holes, therefore, was approximately I:6. During the year, 1890 wells were completed in eastern and western Kansas. This figure is somewhat lower than that given in several trade journals, because it does not include wells that were deepened or wells that were recompleted in a different geological horizon. About three fourths of these (1423) were completed as commercial oil wells (I220 in western and 203 in eastern Kansas). The commercial gas wells completed number 58 of which 10 are in eastern Kansas and 48 in western Kansas. Of the remzining completions 147 are dry holes in eastern and 262 are dry holes in western Kansas. Based on daily potential capacity, the new discoveries of the year account for a cumulative initial production of 46,000 bbl. in eastern and 2,128,000 bbl. in western Kansas. The state of Kansas attained a new peak in production, with the total of 66,245,000 bbl. for the year 1940, the number of contributing wells being 20,779. Thus the increase over 1939, when about 58 million barrels was produced, is considerable. The previous peak occurred in 1937, when 70,761,000 bbl. was marketed. In another still earlier peak, in 1917, slightly more than 45,000,000 bbl. was produced and sold. The production of gas probably reached a new peak also during 1940, with its total of 85 1/2 billion cubic feet. Between the peak of the year 1908, when over 80 billion cubic feet was produced, and that of 1940, the production dropped to a low point of 16 billion cubic feet in the year 1921. The number of test wells drilled was larger than in 1939; that is, 1890 compared with 1458. The first peak was reached in 1904, when 2782 wells were drilled. The number dropped off rapidly, to 368 three years later, but rose to the second and highest peak in 1918, when 4671 test wells were completed. In the period between 1904 and 1912 more gas wells were completed than oil wells. Between the high peak of completions in 1918 and somewhat lower peak of 1937, the low point was reached during 1931, with the completion of only 470 test wells. In the number of new pools discovered, Kansas again ranks high among the states. The exact number depends somewhat upon the interpretation of a "new" area— whether it should be called a new pool or a long extension of an old pool. Unfortunately, the matter of securing the right kind of production allowable also enters into this question. Often the decision regarding a new pool cannot be made until other wells

Jan 1, 1941

By W. A. Ver Wiebe

The year 1940 was singularly unmarked by sensational developments in Kansas. Routine operations were carried on in a systematic, orderly fashion and the efforts of oil producers were concentrated on extending known fields. In Kansas an arbitrary yardstick for wildcats has been set up. A well drilled mile or more from a known pool or well is now considered a wildcat. A "rank wildcat" is one that is drilled at least 2 miles from any known producer. During 1940, rank wildcats resulted in the completion of 116 test wells, among which 16 were successful in finding new oil pools and the remaining I00 were dry holes. The ratio of successful wells to dry holes, therefore, was approximately I:6. During the year, 1890 wells were completed in eastern and western Kansas. This figure is somewhat lower than that given in several trade journals, because it does not include wells that were deepened or wells that were recompleted in a different geological horizon. About three fourths of these (1423) were completed as commercial oil wells (I220 in western and 203 in eastern Kansas). The commercial gas wells completed number 58 of which 10 are in eastern Kansas and 48 in western Kansas. Of the remzining completions 147 are dry holes in eastern and 262 are dry holes in western Kansas. Based on daily potential capacity, the new discoveries of the year account for a cumulative initial production of 46,000 bbl. in eastern and 2,128,000 bbl. in western Kansas. The state of Kansas attained a new peak in production, with the total of 66,245,000 bbl. for the year 1940, the number of contributing wells being 20,779. Thus the increase over 1939, when about 58 million barrels was produced, is considerable. The previous peak occurred in 1937, when 70,761,000 bbl. was marketed. In another still earlier peak, in 1917, slightly more than 45,000,000 bbl. was produced and sold. The production of gas probably reached a new peak also during 1940, with its total of 85 1/2 billion cubic feet. Between the peak of the year 1908, when over 80 billion cubic feet was produced, and that of 1940, the production dropped to a low point of 16 billion cubic feet in the year 1921. The number of test wells drilled was larger than in 1939; that is, 1890 compared with 1458. The first peak was reached in 1904, when 2782 wells were drilled. The number dropped off rapidly, to 368 three years later, but rose to the second and highest peak in 1918, when 4671 test wells were completed. In the period between 1904 and 1912 more gas wells were completed than oil wells. Between the high peak of completions in 1918 and somewhat lower peak of 1937, the low point was reached during 1931, with the completion of only 470 test wells. In the number of new pools discovered, Kansas again ranks high among the states. The exact number depends somewhat upon the interpretation of a "new" area— whether it should be called a new pool or a long extension of an old pool. Unfortunately, the matter of securing the right kind of production allowable also enters into this question. Often the decision regarding a new pool cannot be made until other wells

Jan 1, 1941

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By Chas. Y. Clayton, Francis B. Foley, W. E. Remmers

DuRing the summer of 1919, the late Dr. Henry M. Howe, then Chairman of the Division of Engineering of the National Research Council, organized a committee to obtain a better insight into the behavior of carbon steels under the influence of various treatments by a proper control of the time and temperature factors. During part of 1919 and 1920, work in connection with this investigation was carried on at Dr. Howe's laboratory at Bedford Hills, N. Y. During 1921 there was an enforced hiatus in the work, occasioned by the illness which resulted in Dr. Howe's death in 1922. At that time one of the present authors compiled the results of the work which had been done and this was published in 1923.' Following the publication of this work, it seemed desirable to carry on in the same manner an investigation of steel of C 0.75 per cent., which steel had not been as fully treated as had the other steels of C 0.34 and 0.52 per cent., used in the published work. Furthermore, certain unusual results have been obtained in the treatment of C 0.52 per cent. steel by quenching and drawing, and repetition of this part of the work seemed advisable. This has been done during the past year at the School of Mines and Metallurgy of the University of Missouri at Rolla, Mo., by a cooperative undertaking of the School and the Bureau of Mines, working in conjunction with the Committee on Heat Treatment of Carbon Steels of the National Research Council. The present paper is a report of the results obtained in this work.

Jan 1, 1926

By E. J. Ripling

TUBES may be produced by a large number of forming processes, the most common of which will be discussed analytically in this paper. In no case will the stress analysis for any given tube producing process be derived formally for where such analyses are available, they may be referred to readily. Rather, emphasis will be placed on the interpretation of the theory of the different processes, few of which are developed to a state that will allow rigorous mathematical analyses, in an attempt to give a rational description of the effects of the different variables involved in each method. Tube producing methods can be divided into two groups: Those used to form shells, and those used to further work these shells into a shape more suitable for their final use. Among the first group are included roll piercing, extrusion and cupping for seamless shells, and bending with welding for welded tubes. The re-forming processes include sinking, drawing with a plug, and drawing with a rod. Only the plastic forming operations will be discussed here; other forming processes such as casting shells will not be considered. PRODUCTION OF SHELLS Shells for Seamless Tubing Piercing: The extremely important process of forming an axial hole in a billet by oblique rolling never has been analyzed satisfactorily, although a certain amount of experimental work relating to this process has been conducted. There are a number of factors that make piercing difficult to analyze; one of these is the fact that piercing is not a problem in plasticity, but one in fracturing, and the laws of fracturing are even less well understood than those of plasticity. If, however, it is assumed that fracturing occurs on a surface as a result of tensile stresses acting normal to this surface, piercing can be analyzed qualitatively by examining the stresses established in the oblique rolling process. To determine the origin of the tensile stresses that are thought to effect piercing, it will be necessary to know the angular relationships between the maximum stresses that are established in piercing. These angles quite frequently can be determined in a plastic deformation process by an examination of the deformed product. For example, consider the stresses established when a tensile test is conducted on a rectangular cross-sectional specimen of pearlitic steel. When stretched, this material first flows plastically, exhibiting the well-known yield jog on a stress-strain curve. The formation of the slip areas that give rise to the yield jog can be detected during the straining, since these flowed areas cause depressions on the specimen surfaces which can be seen if the surfaces are polished highly. The plastically strained areas also can be found after the specimen has been stretched to a strain not exceeding the yield jog, by sectioning the test piece and. etching these sections with Fry's etch. With this etchant, it is possible to dis-

Jan 1, 1951

By George Lehman

THE Inspiration Consolidated Copper Co. had an orebody at Miami, Ariz., of close to 100,000,000 tons of low-grade copper ore, and the method of mining this ore most profitably was of great importance. The selection of a method was practically limited to a "top-slicing," a "shrinkage-stope" or a "caving" method. The "top-slicing" method would give a high extraction of the developed ore, at a high mining cost, and the ?shrinkage-stope" or "caving" methods ) a lower extraction of, the developed ore, at a lower mining cost. ORE-DRAWING TESTS To decide on the method to be used it was necessary to know about what extraction of the ore could be obtained by the "shrinkage-stope" or "caving" methods. As no definite information regarding the question was available at the time, C. E. Mills, the general manager, thought that some information could be obtained by experimenting in drawing ore, covered with capping, from an experimental box. Some work had already been done along these lines by W. C. Browning for the Inspiration Copper Co. and by myself for the Live Oak Development Co. The idea was to represent as nearly as possible, in the experimental box, the conditions within an area of caved stopes of caved ore all ready for drawing. That is, the area was supposed to represent a semibroken mass with the capping above it in the same condition and ready to follow the ore downward as it was drawn out of the chutes under the ore. To represent the above condition, in the experimental box, crushed ore from the mine was placed in it to a given height, and red barren capping from the mine was placed on top of the ore.

Jan 9, 1916

By L. Guttman, C. S. Barrett, J. S. Bowles

THE transformation from the face-centered cubic (Al) to the face-centered tetragonal (A6) structure in certain alloys of the indium-thallium system reported in the preceding paper1 exhibits many interesting crystallographic and metallo-graphic features, most of which presumably are similar to those of other cubic to tetragonal transformation such as, for example, the one which occurs in the chromium-manganese system,2 the one which, judging by microstructures and X-ray pat-terns,3 probably occurs in the copper-manganese system, the ones accompanying ordering in FePt,4 Copt,&apos; and AuCu,5 and the transformation near 115°C in barium titanate.6,7,8 If, as mentioned in ref. 1, the transformation is second order, the phases in equilibrium do not differ in composition, and it is both possible and likely that the mechanism is a diffusionless one. The present paper reports the results of a detailed study of the indium-thallium transformation and presents a theory for the atomic movements of the transformation which accounts for the observations. Experimental Crystallography of Transformation Markings The transformation from cubic to tetragonal in the indium-thallium alloys produces microstruc-tures of the type illustrated in fig. 1. These structures are observable either as relief effects produced on a smooth surface by the transformation, or after polishing and etching. These microstruc-tures are markedly similar to those found in copper-manganese alloys: iron-platinum alloys," and barium titanate,7,8 where it has been demonstrated that the lamellae are parallel to the (101) planes of the original cubic crystal. That the observed lamellae in indium-thallium alloys are also parallel to the (101) planes was proved by the following analyses performed on single grains in polycrystal-line samples containing 20.75 atomic pct T1. A study of the microstructures of a number of specimens revealed the fact that in many specimens the transformation markings continued unchanged in direction across the (111) interfaces of annealing twins. This at once demonstrates that the lamellae are parallel to a plane that is common to both parent and twin orientations, i.e., a plane in the zone <112>. This conclusion is compatible with the lamellae being parallel to (101) planes. To make a more complete determination of the habit plane of the lamellae, two grains were selected in which annealing twins ({Ill) twins) had been present in the high-temperature modification (cubic). The traces of the annealing twins, and of the transformation markings in both parent and twin crystals, were plotted together in stereographic projection, and a parent-twin pair of orientations was found that accounted for all lamellae as (101) planes. The projection of one of these twinned grains is reproduced in fig. 2. In view of these results the probability of there being another solution for the habit plane remote from (101) is very small, but to explore the possibility that the habit plane deviates slightly from (101), a more precise analysis was undertaken. In this, the orientation of a grain in the cubic modification was determined from a Laue back-reflection photograph taken with the sample at 90°C. The traces of the lamellae that formed in this grain on cooling were plotted in the stereographic projection

Jan 1, 1951

By Gordon M. Yocom

A PROPER consideration of the subject of this paper should include economic aspects as well as the technical phases of the metallurgy, production, and properties of the product. The metallurgical phases of the processing and properties of the product will be considered only from practical aspects and within the scope of the writer&apos;s experience with tonnage production. The Bessemer process was invented 85 years ago and became important because it put steel manufacture upon a larger and less costly basis. In America the Bessemer production has declined for many years and has not maintained its proportionate place with the rapid advances of the open hearth. The achievements in the open-hearth field were attained by the greater number of technical people attracted to that branch of the industry. The antipathy of technical students for the older and less popular Bessemer field gradually weakened the forces defending it and retarded the development of new and better methods. In Europe the economic advantage of the basic Bessemer process has not been overlooked and the tonnage usually is greater than that of the open hearth. The acid process has been the subject of renewed attention in America during the past few years and those who are more familiar with it are striving to show that the method is too valuable to abandon. A considerable tonnage of Bessemer-blown metal, in both molten and ingot forms, used in connection with the open-hearth practice makes it an important auxiliary unit to the industry. This practice aids in modifying the price level of heavy remelting scrap in addition to speeding up the open-hearth operation. The use of Bessemer steel has continued not only because of periodic economic advantages but also because of certain inherent qualities of machinability, weldability and stiffness, which are valuable for many applications. The properties of stiffness and rather high reaction to cold-work require some modification in order to meet the demands of modern methods of processing, which involve cold-reduction and cold-forming. At least one factor contributing to the stiffness of this steel is the relatively high phosphorus content of the acid product. The phosphorus content of the Thomas or basic Bessemer steel of Europe is considerably lower than the normal acid product in America. The American industry has continued the use of the acid process chiefly for the reason that the available ores are more easily adapted to this process from both metallurgical and economic standpoints. In European practice the basic process is necessary with the highly phosphoric ores available and it is sustained to some degree by the sale of the rich phosphate slag as a by-product. The basic process was used in this country at several plants many years ago, but was abandoned for economic reasons. A part of the past history of these trials is given here because the author believes it has not been published and it has some bearing on the subject of this paper. The information is authentic to the extent that

Jan 1, 1941

By R. B. Muter, W. C. Grady, T. D. Wheelock, D. G. Chedgy

INTRODUCTION Topics of special interest, such as preparation plant flowsheets and noise pollution, are described in this chapter along with a discussion of non- state-of-the-art processes such as chemical cleaning, high intensity magnetic separation, and bacterial oxidation. PREPARATION PLANT FLOWSHEETS by RICHARD B. Muter In determining the layout or combination of unit operations to be utilized in a modern preparation plant several factors must be taken into account.

Jan 1, 1979

By G. W. Healy, W. D. Forgeng, N. R. Griffing

The liquidus surface of the C-Cr-Fe system to 1900°C has been mapped from carbon solubility and freezing point measurements, metallographic observations, and published data. In the graphite field, the surface drops precipitously to meet a slope descending from the Cr3C2-C join through the mixed carbide fields to a meandering eutectic valley; this flows from the Cr-C to the Fe-C edge. On the low-cavbon side of the valley, the surface rises to the chromium corner. 1 HE purpose of this inquiry was to gain a more complete knowledge of the C-Cr-Fe liquidus surface. This required an extensive study of carbon and chromium-rich alloys which, in the past, have received the least attention. Sanbongi el al.1 measured the solubility of carbon in liquid alloys containing up to 25 wt pct Cr at temperatures of 1460" and 1545°C and found that it increased with chromium content and temperature. Lucas and wentrup2 also made solubility experiments in graphite crucibles, but at higher chromium contents in the range of 38 to 80 pct and at temperatures of 1550" to 1700°C; however, their experiments were relatively few, and the effect of temperature was not consistent. The present investigation included compsitions ranging from 0 to 94 pct Cr and 1.4 to 11.7 pct C at temperatures up to 1800°C. Saturation experiments in graphite crucibles, thermal analyses during freezing, and metallographic and X-ray diffraction studies were employed to obtain desired information which, together with published data from other investigations about the binary edges and the ternary system at lower carbon levels, made possible the construction of a comprehensive C-Cr-Fe liquidus surface. C-CR-FE LIQUIDUS SURFACE The derived ternary liquidus surface is shown in Fig. 1 where the solid curves are liquidus isotherms. The dashed curves and the binary edges are the liquidus field boundaries of the primary crystals, the arrows along these boundaries indicating their direction with decreasing temperature. Each intersection of three internal boundaries is the composition of liquid involved in four-phase isothermal equilibrium with the three primary crystals whose liquidus fields touch there. It may be observed that a total of six four-phase equilibria occur at melt temperatures. The general topography of the liquidus surface consists of a eutectic valley sloping down from the Cr-C edge at 3.2 pct C to the Fe-C edge at 4.25 pct C. The liquidus surface rises in two directions from the valley, one hillside terminating at the Cr-Fe edge while the opposing hillside rises toward the carbon corner out beyond the top edge of Fig. 1. Both hillsides are interrupted by intersections of surfaces or joints representing the liquid colmpositions of various three-phase equilibria. Seven primary crystals occur, namely a(bcc), ?(fcc), graphite, (Fe, Cr)3C capable of dissolving as much as 15 pct Cr, and three different chromium carbides in which iron is partially soluble by substitution for chromium. The composition ranges of the primary l~hases at melt temperatures are shown

Jan 1, 1962

By Y. C. Liu, G. A. Alers

The anisotropy of Young&apos;s modules has been measured in a series of Cu-Zn alloys containing from 1 to 28 wt pct Zn and cold-rolled to 97.5 pct reduction in thickness. These modulus data show a transition in texture as a function of zinc content. In alloys containing 3 pct Zn or less, the texture is essentially that of copper. A transition is clearly seen to develop in 5 and 8 pct Zn alloys, and to have been completed in a 12 pct Zn alloy. Increasing the proportion of zinc to 28 pct does not produce any further changes in texture. The ease and clarity with which this texture transition can be seen in the modulus data is in great contrast with the inccertainty in the visual detertiination of the range of texture transition from a series of pole figures. It is also shown that the rolling texture of the high zinc content alloys cannot be a one-COIIIponenl texture, characterized by the (110)(112) ideal orientations, as usually assumed. A second, quite important component must also be present. Furthermore, the present data are inconsistent with matrix orientations on which the "oriented growth" hypothesis of the Formation of recrystallization textures is based. THE rolling textures of binary fcc alloy systems have generally been considered to lie between two terminal textures. One of these terminal textures is the copper type and the other is the 70:30 brass type. Alloys of intermediate solute content exhibit a texture which is said to be a transition between the two terminal textures. On the basis of efforts to correlate rolling and recrystallization textures, two concepts have been advanced in the literature on the nature of these transition textures. One school1 suggests that the addition of alloying elements, e.g., zinc, causes a gradual rotation about one of the (111) poles from the (358)( 523) ideal orientation of the copper-type rolling texture to the terminal {1 10)( 112) ideal orientation used to describe the rolling texture of 70:30 brass. This concept is depicted in Fig. 1 with the angle of rotation corresponding approximately to the zinc content and is designated here as the "rotational concept", since the ideal orientation of the transition textures varies continuously with alloy content. The other concept,&apos; the "mixture concept", suggests that the copper-type rolling texture is a two-component texture. {358) (523) and {110)(112). The addition of alloying elements affects only quantitatively the relative amounts of these two components—a decrease in the amount of material in the {385}(523) orientation and an increase of that in the {110)(112) orientation with increasing solute content. An experimental distinction between these two concepts is essential to a better understanding of both the mechanism of formation of rolling textures and the subsequent formation of recrystailization textures in fcc metals. Because of the lack of resolution inherent in pole figures, it has not been possible to differentiate between the two concepts on the basis of this data. Both concepts, in fact, make use of the same set of pole figures but interpret them in a manner acco-rding to the view held.&apos;" Experimental results obtained from inverse pole figures or selected-area electron diffraction3j4 simply -yield more refined pole figures but do not eliminate the ambiguity of interpretation. Quantitative measurement of an entirely different, orientation-dependent property must thus be considered

Jan 1, 1967