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By R. P. Fischer

A large production of vanadium during the war helped Germany to meet her critical requirements for the ferroalloy metals. Vanadium was needed not only in the ordinary high-speed too1 steels, but in other as a substitute for chromium, nickel, and molybdenum, which were scarce. Lacking a source of vanadium ore, however, the vanadium was obtained as a by-product of the steel industry—va-nadium-bearing pig iron smelted from iron ores containing about o. I per cellt V was blown in converters to yield vanadium-rich slag, from which vanadium was recovered by chemical treatment. The production capacity obtained was said to be about 6,500,000 lb. of vanadium a Year. Although the general Processes of Preparing vanadium-rich slags as well as the recovery methods described herein are known, some of the details presented may be of interest to both the American steel industry and the vanadium producers. No adequate data on the cost of the vanadium produced in Germany are known, but it seems likely that the cost exceeds the commonly quoted domestic price of about $1.10 per pound of contained VzOa. Information on the German vanadium production was obtained by a team of geologists from the Geological Survey* United States Department of the Interior, during investigations in May and June 1945 of the German utilization of low-grade raw materials. These investigations were sponsored by the Chief of Engineers, War Department. It is a pleasure to acknowledge the aid obtained from Messrs. H. C. Smith and J. D. Dickerson, investigators assigned to the Army Ordnance section of C.I.O.S., and Mr. C. F. Park, Jr., of the Geological Survey team. The data on vanadium recovery from iron ores were obtained from the Kaiser Wilhelm Institut fiir Eisenforschung, the Hermann Goring steel plant at Watenstedt, and from notes made by other investigators at other German steel plants. Preparation of Vanadium-rich Slags Most German iron ores contain only about 0.1 per cent vanadium, or even less, but some of the scandinavian iron ores available to the German iron industry in the past contain a little more than 0.1 per cent. In general German practice of vanadium recovery, nearly all of the vanadium in the ore goes into the pig iron, which is blown in the Thomas converter, yielding a slag containing about I per cent V. This slag is remelted, the vanadium again going with the iron, which is again blown in a converter, yielding a slag that averages about 10 per cent V. This slag is treated at special chemical plants, by the process of a sodadizing roast, water leach, and acid precipitation of vanadium oxide. The Herman Goring steel plant at Watenstedt used the low-grade Salzgitter iron ores, the average composition of which is shown in Table I, column I. The acid and basic iron produced in the blast furnaces contained about 0.3 per cent V. A Thomas

Jan 1, 1948

By N. J. Grant, Hans Brunner

ThE materials used in this investigation were furnished by the Aluminum Co. of America and consisted of high-purity alurhinum (99.995 pct) and two aluminum-magnesium alloys containing approximately 2 and 5 pct Mg. The compositions of these alloys are listed in Table I. The materials were received as hot rolled 3/8-in. diam rods and were made from the same heats as the materials which were previously used in this laboratory.'j3 The rods were cold swaged to 1/4-in. diam by 1 in. long, and then had two parallel flats machined over the gage length 0.085 in. apart. The test bars were annealed for 10 min at 700° F, and strained 1 pct in tension at room temperature. They were electropolished (80 pct acetic acid; 20 pct perchloric acid, 70 pct concentration) at a temperature of 60°F at approximately 20 v. A grid, transverse or square, spaced 0.2 mm apart, was impressed by rolling a fine threaded screw (128 threads per in.) across the flat surfaces. The depth of the grooves was less than 5 p. For final annealing and grain size control the specimens were enclosed in aluminum foil and sealed in Vycor tubes. Annealing conditions varied from 1 hr at 700° F to 5 days at 1050° F, depending on the alloy content, to give for most of the specimens a final grain size of about 1 mm. This treatment was followed by electropol-ishing as described above. For the test series presented in Figs. 4 and 5 round specimens were used instead of flat ones, and fine machining marks served as marker lines instead of the impressed grid lines. Electropolishing was omitted. The major advantage is that the spacing of the machining marks is only about 1 u as compared to the 200 u of the impressed grid lines, permitting higher precision in strain measurements. Unfortunately the strain annealing necessary for grain size control also resulted in some preferred orientation of the grains. The preferred orientation of three arbitrary specimens was measured by X-ray diffraction methods and the averaged results are shown in Fig. 1. The possible effects of the preferred orientation on the test results will be discussed later. The testing temperatures were 410°, 515", 725", and 940° F, with one exception in the case of the 5.1 pct Mg alloy. Since the solubility limit of this alloy is 520°F, a test temperature of 545°F was cho-se sen instead of 515°F. The selection of the test temperature was based on two considerations: 1) at 900°F and above, extensive grain boundary migration made it more difficult to measure grain boundary sliding; 2) at 400°F and below, there was so little grain boundary sliding that it was again difficult to make precise measurements. The stress was chosen to give a creep rate of approximately 2.7 pct per hr in connection with Figs. 2

Jan 1, 1961

By A. Raman

The Nb-Co system was nuestigated in the range 10 to SO at. pct Co with X-rays. A pt phase with the W6Fe.r-type structure occurs in the system between 46 and 52 at, pct Co. Its unit-cell dimensions are nearly identical to those of the p Phases found in the Nb-Fe and Nb-Ni systems. Two Laves phases, one having the MgZnz-type structure and the other the MgCuz-type structure, already t-eported in the literature, are found to exist in the system. The ,l.IgZnz-type phase occurs between 62 and 64 at. pct Co. A MgNi2-type Laves phase, reported in the literature, is no! obtained. A binalry phase is found to exist belozv I000C around 82 at. pct Co. THE cobalt-rich side of the system Nb-Co has been repeatedly investigated by previous inestiators" and the following intermediate phases are known to occur: NbCo, which crystallizes in the MgCu2-type structure and Nbc03,' reported originally by Wall-bam, which has the MgNiz-type structre. Jordan and uwez' as well as lliott' were unable to find the MgNiz-type phase. Two phases, designated as x and y, were reported by Saito and eck.' The phase x was inferred to have a narrow composition range near 77 at. pct Co. No published work is known to the author which reports the investigations in the niobium-rich portions of the system. This paper presents the results of an investigation in the Nb-Co system between 10 and 80 at. pct Co. EXPERIMENTAL PROCEDURE Two or three grams of the alloys under investigation were prepared using niobium (99.9 pct +) and cobalt (98.8 pct + with 0.14 pct Fe and and 0.03 pct C) in a tungsten-electrode arc furnace under commercial argon atmosphere. They were then wrapped in molybdenum sheets and annealed for a period between 5 days and 1 week at 1300°C in high vacuum (10-" orr) or in evacuated quartz amules for 2 weeks at 1000°C. Powders of -325 mesh size were prepared for X-ray work by crushing and grinding the specimens. Subsequent reannealing of the powders was not undertaken since most of the alloys were brittle and broke easily. X-ray powder patterns of the as-cast and annealed samples were prepared in a Siemens cylindrical camera (57.3 mm radius) with Cr-K, radiation. A Siemens diffrac to meter was used to get the X-ray patterns of some new phases. Metal log raphic examination of the alloys supplemented the X-ray findings. RESULTS The results of the X-ray and microstructural analysis Of the alloys are in in Table I. The lattice parameters of the phases are listed in Table 11 for quick reference. A set of micro photographs in Fig. l(n) to (j) show the microstructures of some alloys. A probable equilibrium diagram is drawn in Fig. 2

Jan 1, 1967

By H. F. Yancey, M. R. Geer, C. L. Allyn, R. H. Eckhouse

W. M. Bertholf—This is an excellent report of a well-conducted investigation, of sufficient scope to provide generally useful information. Some years ago we had occasion to test the Humphreys spiral on the middling from our table plant. The conclusions reached in this investigation come as no surprise to us. In certain applications it is virtually impossible to improve on the spiral from the monetary returns point of view even though its "efficiency" may be low. We have noted that in all successful applications of the spiral the feed is "classified," hence we were somewhat disappointed in the showing the spiral made on the Poplar Ridge coal, the only one of the four which could really be considered the equivalent of a classified feed. As was noted in the paper, however, this coal contained a considerable amount of middle and high-gravity material, apparently more than enough to make up for the theoretical advantage of small particles in these categories. A comparison of particle size in the various specific gravity classes of the four coals is given in table XXV. Table XXV. Comparison of Particle Size in Various Specific Gravity Classes. (Unit size, 150 m to 0.105 mm) Black Eagle Clements Poplar Ridge Rosly,n 1.3 Float 7.47 10.60 8.68 9.66 1.3 x 1.4 7.89 7.96 7.58 8.20 1.4x1.6 7.24 8.36 5.58 6.85 1.6 x 1.8 7.98 8.31 3.42 7.33 Sink 1.8 7.85 7.13 5.09 7.41 Avg 7.69 10.08 7.15 8.38 This tabulation indicates that there was very little difference in the size of the various gravity fractions for three of the coals, Poplar Ridge varying the most. Examination of figs. 3, 6, 7, and 8 reveals a general similarity of behavior for all coals except Black Eagle. Would the authors care to speculate on the reasons for the difference in the distribution curve for the sink 1.60 material in the washed coal of fig. 3 as compared to the others? This difference is particularly noticeable in the 8xl4-mesh size. Was there a "shape effect"? J. D. Price and W. M. Bertholf—The performance data on three of the coals studied appear to be typical, but there are certain departures from the general pattern in the case of the Poplar Ridge coal which are large enough to deserve special consideration. For example: 1. Despite the high proportion of sink 1.60 material in the feed, it was not possible to make a corresponding proportion of high-ash reject. (See table XVI.) 2. Even though approximately 70 pct of the feed was 1.40 float with an ash content of 6.6 pct, and this

Jan 1, 1951

By R. H. Eckhouse, M. R. Geer, H. F. Yancey, C. L. Allyn

W. M. Bertholf—This is an excellent report of a well-conducted investigation, of sufficient scope to provide generally useful information. Some years ago we had occasion to test the Humphreys spiral on the middling from our table plant. The conclusions reached in this investigation come as no surprise to us. In certain applications it is virtually impossible to improve on the spiral from the monetary returns point of view even though its "efficiency" may be low. We have noted that in all successful applications of the spiral the feed is "classified," hence we were somewhat disappointed in the showing the spiral made on the Poplar Ridge coal, the only one of the four which could really be considered the equivalent of a classified feed. As was noted in the paper, however, this coal contained a considerable amount of middle and high-gravity material, apparently more than enough to make up for the theoretical advantage of small particles in these categories. A comparison of particle size in the various specific gravity classes of the four coals is given in table XXV. Table XXV. Comparison of Particle Size in Various Specific Gravity Classes. (Unit size, 150 m to 0.105 mm) Black Eagle Clements Poplar Ridge Rosly,n 1.3 Float 7.47 10.60 8.68 9.66 1.3 x 1.4 7.89 7.96 7.58 8.20 1.4x1.6 7.24 8.36 5.58 6.85 1.6 x 1.8 7.98 8.31 3.42 7.33 Sink 1.8 7.85 7.13 5.09 7.41 Avg 7.69 10.08 7.15 8.38 This tabulation indicates that there was very little difference in the size of the various gravity fractions for three of the coals, Poplar Ridge varying the most. Examination of figs. 3, 6, 7, and 8 reveals a general similarity of behavior for all coals except Black Eagle. Would the authors care to speculate on the reasons for the difference in the distribution curve for the sink 1.60 material in the washed coal of fig. 3 as compared to the others? This difference is particularly noticeable in the 8xl4-mesh size. Was there a "shape effect"? J. D. Price and W. M. Bertholf—The performance data on three of the coals studied appear to be typical, but there are certain departures from the general pattern in the case of the Poplar Ridge coal which are large enough to deserve special consideration. For example: 1. Despite the high proportion of sink 1.60 material in the feed, it was not possible to make a corresponding proportion of high-ash reject. (See table XVI.) 2. Even though approximately 70 pct of the feed was 1.40 float with an ash content of 6.6 pct, and this

Jan 1, 1951

Edgar Archibald Collins was born at Truro, Cornwall, Nov. 16; 1877. He was the fifth (and youngest) son of J. H. Collins, a well known Cornish geologist and engineer, who died in 1916. Edgar Collins spent part of his childhood at Rio Tinto, in Spain, and after returning to England was educated at Alleyne's School at Dulwich, near London. His technical training was acquired by practical experience in Cornwall, supplemented by private study and by his father's teaching. This method of training for the work of a mining engineer was preferred by his father to that of the technical schools then available, and judging by its result, was not unsuccessful. It is,-however, noteworthy that all members of the Collins family who were products of this system later sent, or planned to send, their own sons to technical schools. Edgar Collins came to Gilpin County, Colorado, in 1894, and returned there in 1898, after several intermediate years spent in Cornwall. In Colorado he worked, under his brother Arthur, in the California and other mines of the Gilpin County district, and thereby gained a practical skill and experience as a working miner, and a habit of minute observation of vein phenomena, which proved of the greatest value in later years. In 1899 he went to the Smuggler-Union it Telluride, as general assistant to his brother Arthur, and stood the brunt of 3 years of struggle with the Western Federation, gaining a reputation, for quiet courage and sound work under the most difficult conditions. After Arthur Collins' assassination in the Smuggler-Union office, in November, 1902, Edgar left Telluride, and shortly thereafter entered the employment of a syndicate headed by Arthur Winslow, of Boston, to search for and develop new mines. While so engaged he spent several unsuccessful months near Parral, in Mexico, and later visited and sampled the- newly discovered district of Grandpa, afterward known as Goldfield, in Nevada. This led to the acquisition by the Winslow syndicate of the Combination mine, at first under lease and option; and Edgar Collins was placed in charge. The Combination was really the starting point of Goldfield. It was a profitable mine before the discoveries at the Jumbo were made; and while the Combination, being a "Company-account" mine, controlled by a few responsible men, never attracted the publicity that centered around the sensationally profitable leases on the Jumbo and Mohawk, which publicity was used to further the feverish stock-dealings that characterized the new district. The Combination was really the pioneer mine, made the first shipments of rich ore, constructed the first water-line, and built the first mill (designed by F. L. Bosqui, an old friend and associate); and while it pursued a quiet and unobtrusive. career up to the time of its sale to and incorporation with the Goldfield Consolidated, was probably, in ;proportion to the amount of money risked, the most profitable bonanza in the recent history of gold mining.

Jan 11, 1918

By L. C. Brown, J. S. Kirkaldy

AS part of a program to investigate the diffusive properties of dilute ternary austenites, we have made a determination of the effects of cobalt on the activity of carbon in y iron. Samples of pure iron and Fe-Co alloys were equilibrated at 1000°C in controlled CO-C02 atmospheres, following the procedure of R. P. smith.' The 0.010-in.-thick samples were analyzed for carbon by microcombustion analysis2 to give a set of isoactivity curves. The latter were converted to activity-coefficient (standard state at infinite dilution) plots by combination with Smith's data' for the activity of carbon in pure iron measured in a CO-C02 mixture. Table I shows the composition of the base alloys used, while Fig. 1 shows the experimental results superimposed on a set of curves generated by the relation In the notation of Wagner,' the interaction parameter is the second coefficient on the right, Eq. [I] adequately correlates the experimental points for those alloys which were prepared from electrolytic iron by arc-melting (2,4, and 7 pct Co). The results for the 10 pct Co alloy (supplied by Crucible Steel Co.) do not correlate with the others. In fact, the experimental points for this alloy correspond to an interaction parameter of It is possible that the interaction parameter is a function of concentration for large cobalt additions, but we are inclined to attribute the discrepancy to the presence of a significant amount of aluminum added to this alloy for deoxidation purposes (Table I). Preliminary measurements for the system Fe-C-A1 have indicated an interaction parameter of Which implies that the effect of aluminum in solution on the carbon activity is sixty times greater than the effect of an equal weight percentage of cobalt. These observations cast some doubt on the precision of the results of Chandhok, Hirth, and Dulis who used this same 10 pct alloy for their experiments, obtaining an interaction parameter of E = 2.2. There is considerable doubt as to the activity of a plane Fe-C system. Using a CH4-Ha mixture, Smith obtains cg = 6.1 for the effect of carbon on the activity of carbon in austenite, rather than the value of 8.9 given in Eq. [I]. The use of CHa-Ha mixtures has recently been questioned by Kaufman, Radcliff, and cohens who state that there is some possibility that other hydrocarbons are formed. Fortunately, the determination of the interaction parameter is not sensitive to the coefficient of Nc. For example, using the CHI-H2 results we obtain a value which is almost the same as that obtained using the CO-CO, results. The authors wish to thank Mr. E. J. Dulis of the Crucible Steel Co. of America for supplying us with samples of the 10 pct Co alloy used in their original work. Financial assistance from the American Iron and Steel Institute is gratefully acknowledged.

Jan 1, 1963

A general discussion on the subject of Crushing and Grinding was held on August 24, 1927, during the meeting of the Institute at Salt, Lake City. G. H. Clevenger, Chairman of the Milling Methods Committee of the Institute, made the following introductory remarks "Several years ago, a number of us felt that the time was ripe for a fundamental investigation of crushing and grinding. At the outset, it appeared that the first thing we needed was a yardstick whereby grinding efficiency could be measured. "The U. S. Bureau of Mines has been most generous in cooperating with the Milling Methods Committee in getting this work well undrr way. John Gross, who served the committee for a year as secretary, was placed in charge of the investigation and has been ably assisted by S. R. Zimmerley. "Messrs. Gross and Zimmerley will now present the Progrcss Report covering their work to date." Progress Report J. Gross, Salt Lake City, Utah.—-This has not been a simple problem, and when I tell you that me can give you a verbal report of what we have done during three years in five or ten minutes you will realize that we have necessarily done a great deal of work that dors riot appear in the final results. We have been in a virtually new field. Therefore, we have had to feel our way at each step so as to be fairly sure we were correet. The first thing that was realized in this problem ass that unless we had some method of measuring what happened when we crushed an ore, we might as well quit and not go further. we realized that if we tried to measure the results of crushing or grinding by the ordiuary sizing test we would not get anywhere. We could sieve down to say 200 mesh fairly accurately; we could even go one sieve size further with a little less accuracy, and then we were absolutely lost, unless we went into microscopic measurement. Even this latter method would not have been satisfactory. The question was: what were we going to measure? If we were going to measure size, we might measure one particular dimension of a particle and be off 200 per cent. or more. If we tried to measure surfaee, we would have something tangible; the surface of a particle, no matter how irregular, is something definite, far more definite than any linear dimension would be. Moreover, if we could measure surface, we would immediately have a method of checking the Rittinger law as to whether it was or was not correct. So the first thing that we sought. was a method whereby we could measure surface on crushed particles or, we will sag., on particles; it would not make any difference whether crushed or not. It then became a question of what kind of particles we were going to use in obtaining a method for surface measurement. We realizcd that it would be rather a corn-

Jan 1, 1928

By J. Suiter, H. F. Ryan

H. F. Ryan and J. Suiter (CSIRO)—In this paper the authors have presented "a physical model which has as its central hypothesis the solution strengthening of regions along grain boundaries in the order of tens of angstroms thick", and their calculations have used 40Å as the zhalf-width of this boundary region. Selection of this value by the authors suggests that they were unaware of a number of recent field-ion microscope observations of grain boundary structures (e.g., Refs. 29 and 30). The accompanying figure, Fig. 9, shows a portion of an ion micrograph of a tungsten specimen containing a grain boundary, and the regular arrangement of atoms in various crystal planes in each grain can be seen, except in the boundary zone which is not more than two atom diameters in width. Since it is expected that solute atoms will segregate only to the region where the lattice is disturbed, it would seem that a value of 4Å for the half-width of the boundary region would be more appropriate than the value of 40Å assumed by the authors. If the former value is used in Eq. [8] of their paper to obtain curves showing solute concentration in the grain boundary as a function of temperature, the resulting curves differ significantly from those obtained by the authors. Although there are only relatively slight changes in the regions corresponding to higher temperatures (i.e., grain boundary concentrations of approximately 1 at. pet), at lower temperatures the curves are no longer realistic. For example, the curve corresponding to u = 7000 cal per mole gives a solute grain boundary concentration in excess of 100 pet at a temperature of approximately 360°K, and "flattens out" at a grain boundary concentration of about 300 pet! Similar results are obtained with each of the other curves. Ion microscopy of dilute solid-solution alloys has shown that solute atoms give rise to image points which in most cases are of higher intensity than those of the solvent atoms.31 If the same behavior occurs when the solute atoms are present in much lower concentrations then ion microscopy should provide a sensitive tool for studying the segregation of impurities to the grain boundary regions. Although many grain boundaries in tungsten have been examined after different thermal and mechanical treatments, there has not been, as yet, any systematic study of such segregation. In general the micrographs show no clear indications of marked grain boundary segregation, but occasionally areas are found where the grain boundary contains an appreciable number of image points of high intensity in a very narrow zone, see Fig. 9. If it is assumed that these correspond to impurity atoms then it is possible to estimate the impurity concentration both in the grain boundary and within the body of the grains. Application of this method (to a larger area

Jan 1, 1965

By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.' In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.' The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.' Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969

By S. Floreen, R. M. Pilliar, H. W. Hayden

The fracture behavior of a 50 pct Cu-50 pct Fe mi-croduplex alloy, laminated composites of copper and iron and an extruded 50-50 Cu-Fe elemental powder composite was studied. Very low ductile-brittle transition temperatures were achieved in all cases, but for different reasons. In the microduplex alloy both the initiation and also the propagation of cleavage fractures appeared retarded by the very small in-terphase distances. In the composites, crack propagation through the sumples was prevented in most cases by delamination fractures perpendicular to the advancing cracks. These delaminations occurred at different regions and by different mechanisms in the various composites. In the extruded powder composite, de-lamination appeared to take place along preexisting flaws. In the crack arrest geometry of the laminated plates, delamination took place by localized shear fractures within the copper near the Fe-Cu interfaces. In this case delamination was enhanced by thicker laminate layers, and by having the resistance to shear failure of the copper sufficiently low compared to the toughness of the iron. BRITTLE fracture in engineering materials has long been a problem, and many different ways of preventing it have been considered. One method that has been of growing interest lately is to prevent crack propagation by the introduction of mechanical discontinuities into the structure. These discontinuities may act in several ways. They may simply act as crack stoppers. They may introduce secondary fractures such as de-laminations that deflect the initial crack into new, less damaging directions. Alternatively, they may subdivide a fairly large bulk sample that would have been loaded in plane strain, for example, into a number of subunits that are individually loaded in plane stress and thus are more resistant to fracture. Other mechanisms, or combinations of mechanisms, are also feasible. A number of methods exist for introducing mechanical discontinuities into a structure. Composites by their nature have discontinuities in structure, and numerous studies have shown that fracture propagation in materials of this type can be radically changed by suitable control of the composite parameters. Of particular significance to the present work are recent investigations of layered composites made by joining high strength steel sheets by various means.'-4 These studies have shown that through proper control of the mechanical properties of the bonds joining the sheets it was possible to introduce delamination fractures that markedly improved the overall toughness of the composites and in some cases completely prevented through-the-thickness fractures. Another technique for introducing structural discontinuities is simply to use a two-phase alloy. It has been recognized for many years that a small amount of a second phase may improve toughness either by homogenizing plastic flow and thus preventing localized stress concentrations that nucleate fracture, or by interacting with an advancing crack. In most of these studies of two-phase materials, the decreases in ductile-brittle transition temperatures produced by the second phase were relatively small. More recently, work on two-phase stainless steels having a very fine grain microduplex structure has shown that the presence of on the order of 40 to 50 pct of a tougher second phase may lower the ductile-brittle transition temperature of the brittle phase by approximately 300°F. 5-7 In these alloys delaminations were seldom observed. The tougher second phase appeared to minimize the ease of both the initiation and the propagation of cleavage fractures. These results show that both the composite approach and the microduplex alloy approach are effective methods of preventing brittle fracture. Therefore, it was of interest to compare the fracture behavior of a microduplex alloy with composites made from the two-phases that were present in the alloy. To simplify this comparison the 50 pct Cu-50 pct Fe system was selected for study. At low temperatures the equilibrium tie line phases in this system are essentially pure ferrite and pure copper. A 50-50 alloy was cast and hot worked to produce a microduplex structure. Two types of composites were studied; laminated structures prepared by roll bonding iron and copper sheets of the tie line compositions, and an extruded powder composite made from high purity elemental powders. The fracture behavior of these materials was then compared. EXPERIMENTAL PROCEDURE Alloy Preparation. The 50-50 Fe-Cu alloy and the components for the roll bonded composites were prepared by vacuum induction melting 30-lb heats using electrolytic grades of iron and copper as charge materials. A carbon boil was used to deoxidize the melts. Small additions of copper and iron were made to the iron and copper heats, respectively, to approximate

Jan 1, 1970

By C. F. Allen, G. B. Walker

The sink-float methods designated by heavy-media separation processes were pioneered by C. Erb Weunsch for the treatment of base metal ores as an improvement over jigs. The work of Weunsch was further developed by Victor Rakowsky and The American Zinc, Lead and Smelting Co. Early in the development of the processes, the inherent unsuitability of galena as the solid constituent of the medium was recognized and ferrous media amenable to magnetic recovery and control were developed. The high efficiency and low cost of magnetic recovery and cleaning of ferrous media regardless of particle size, slime contamination, or surfacial oxidation had led to the adoption of ferrous media by all of the sink-float plants operating under the heavy-media separation processes patents controlled by American Zinc, Lead and Smelting Co. Approximately 2,000,000 tons of base metal and nonmetallic minerals are treated each month by these methods. Heavy-media separation processes are a modern practical and economical adaptation of the well-known laboratory procedure for separating a mixture of two solids by immersing the mixture in a liquid having a specific gravity intermediate the specific gravities of two solids. The lighter solid floats while the heavier sinks. This method of separation has been attempted on a commercial scale, but the high loss and high cost of the organic liquids halted the development of the process. Many attempts have been made to simulate a heavy liquid by using a suspension of a finely divided solid in water. If the solid phase of the suspension is ground fine enough, the suspension can be made stable or so slow settling that a substantially uniform specific gravity can be maintained from top to bottom of the bath. However, any material separated by such methods will inevitably be contaminated by some slime which will eventually accumulate in the bath and cause a viscous medium at the expense of separating efficiency. Therefore, it is necessary to provide means for continually cleaning a portion of the medium to eliminate slime at the same rate at which it is introduced to the medium. The problem of efficiently cleaning the medium limits the minimum grain size of the solid of the suspension in the case of the Chance sand process for cleaning coal, because de-cantation is the only cleaning method available. If the sand is too fine, it will be lost along with the slime. Therefore, coarse sand must be used, and to maintain a semblance of a uniform suspension, it is necessary to use strong rising water currents. The combination results in a separation based more on hindered settling classification than on sink-float principles. As previously mentioned, galena was used as the solid constituent of the medium during the early stages of the development work. The high specific gravity of galena made it suitable for the preparation of medium for high specific gravity separations. Galena can be cleaned by either decantation or by froth flotation. As with sand, de-cantation limits the minimum particle size of the media that can be cleaned without excessive loss. Froth flotation for cleaning galena medium has been used, but the problem of floating fine galena that has been exposed to extensive oxidation is well known to be a most difficult one. Last year the largest heavy-media plant m the world, and the second plant to be installed, converted from galena medium to ferrous medium despite the fact that the ore contains galena which can be used as medium. The change to ferrous medium has been beneficial in many ways. Today all the heavy-media plants have been converted from galena to ferrous media. Unquestionably, ferrous media have the widest application of any media developed, for the following reasons: 1. Ease of recovery and cleaning by magnetic means. Particle size or surface condition not a factor. 2. Low consumption per ton of ore treated. 3. Resistance to abrasion. 4. Widest range of media densities, including higher workable densities (1.25 to 3.4) than have been found possible with nonferrous media. 5. Space required for recovery and cleaning of ferrous media is considerably less than that for nonferrous media. 6. Ferrous media require lower capital investment and operating costs for media recovery and cleaning. Advantages of Heavy-media Separation Processes Heavy-media separation processes offer the following positive advantages, amply demonstrated on a wide variety

Jan 1, 1950

By V. B. Kurfman

Grain refinement of Mg-Al melts by carbonaceous additions has been attributed to nucleation by aluminum carbide. The effects of process and alloy variables are interpreted and predicted in terms of the dispersion and chemistry of this phase. The grain coarsening action of Be, Zr, Ti, R.E., chlorination, temperature extremes, and prolonged holding times is described. Measures necessary to insure an adequate dispersion of the catalyst are discussed. CARBON inoculation treatments have become fairly well known and used for grain refinement of magnesium alloys containing Al. Although there is general agreement that a nucleation process occurs, the process is not understood and the inoculants are used in a rather empirical fashion. The treatment is applied to the class of alloys containing 3 to 10 pct Al, i.e., AZ31A to AM100A. Typical methods involve melting, alloying, and adjusting the temperature to 1400° to 1450°F. Then 0.01 to 0.5 pct C as CaC2, C6C16, or lampblack is added by any convenient means, and the melt poured within 10 to 30 min. Investigators generally have been impressed by an assumed similarity of this refinement process to superheat grain refinement, which depends on heating approximately the same alloys to a temperature in the range of 1550" to 1650°F, then pouring promptly after the melt is cooled to the pouring temperature. Various predictions have been made that carbon refinement would replace superheating in commercial practice due to reduced process costs, but this replacement has not fully taken place because of production difficulties and conflicting observations. Davis, Eastwood, and DeHaven1 agree with Nelson2 and wood3 in suggesting that an excess of inoculant may be harmful. Wood however says that overtreat-ment is not a problem in production use of hexa-chlorobenzene inoculation, and Hultgren and Mitchell4 claim no evidence of harm from excess additions. Various grain coarsening reactions are known to occur, including the possibility of overtreatment mentioned above. Trace amounts of Be,2 Zr, and Ti may prevent refinement by either a carbon treatment or a superheat. Occasionally treatment with cl25 may cause coarsening, although the Battelle refinement process' uses a CC14-C12 blend. Grain coarsening also tends to occur on holding at temperatures below 1350°to 1400°F, especially after a superheat treatment, and for this reason Nelson2 stresses the desirability of a refinement method useful at lower temperatures for open pot melting practice. Since a carbon treatment can be made to work at temperatures below 1400°F, it seems desirable to investigate the mechanism of the refinement and the mechanisms of the coarsening reactions in order to establish control conditions for use in commercial production. The identity of the nucleating phase must first be established and then the factors affecting its chemistry and physical dispersion must be determined. THE IDENTITY OF THE NUCLEATING PHASE Davis, Eastwood, and DeHaven suggested that the nucleating phase in this system is Al4c3,1 but Mahoney, Tarr, and LeGrand8 disagree, largely because they found no evidence of the compound in alloys after carbon treatment and because there is no indication that aluminum carbide should be unstable over the temperature range used in the superheat treatment. This latter objection is based on the assumption that both the carbon treatment and the superheat treatment introduce the same nuclei. Electron diffraction studies have been made to identify the nucleating phase. Samples of grain refined A292 have been selectively etched SO that clean surfaces are obtained and so that secondary phases are in relief. Electron diffraction patterns from these surfaces have established that the carbon treatment of A292 introduces into the metal a large number of small, plate-like particles with a structure very similar to Al4C3. In most cases, the plate-like nature of the particles prevented positive identification but in the cases where the identification could be made the particles proved to be AIN A14C3. However, enough variation in lattice constants was observed so that all compositions from pure A14C3 to the 50:50 solid solution A1N.Al4C3 were probably present.14 In A14C3 and especially AlN.Al4C3 the A1 atoms occur in layers within which they have the same hexagonal symmetry and spacing as the Mg atoms in a single basal plane of a magnesium crystal. The solid solution spacing lies between the 3.16 of AIN and the 3.3? for Al4C3, in satisfactory agree-

Jan 1, 1962

By W. F., Dietrich

THIS paper deals with the- methods of mining the high-grade clays of California. Although the majority of the clay pits in the state are operated on a scale that is small by comparison with most metal mines, this very fact results in a diversity of methods and gives rise to problems of selection of the method best suited to given conditions. Two or three operators in California produce approximately 500 tons per day of a single kind of clay from a single pit. About five varieties of clay are mined on a scale of 200 to 400 tons per day; not over fifteen varieties are mined on a? scale of 50 to 200 tons per day; and more than 50 varieties are mined at a rate of less than 50 tons per day. It is the aim of this paper to delimit, insofar as the data at hand permit, the conditions and scale of operations that favor the selection of each dominant method of mining that is actually being applied at California properties. Details of the occurrence and utilization of the clays of California have been given in a recent bulletin and are not considered here.

Sep 1, 1928

By NEWTON B. KNOX

THE Guianas region is a geological unit, consisting of the northern lobe of the Brazilian Shield, but political accident and the fact that rivers act as the principal means of transportation have divided the region between five separate sovereignties. Brazilian and Venezuelan Guiana have already been considered. The French, Dutch, and British colonies consist of a coastal plain some fifty miles wide, which, together with the lower reaches of the principal rivers, support the greater part of the population. Inland from this tidewater region is a wide area of low, forest-covered hills, under-lain by gneisses, schists, granites, and pegmatites of the Shield. As in Venezuelan Guiana, these rocks are overlain by a thick series of horizontal continental sediments intruded by moderately basic magmas. Gold, bauxite and diamonds have been the principal products of the colonies. The first metal is quite widespread in the hill country. The quartz mines are small, though occasionally rich; probably the greater number of veins remain undiscovered because of the thick mantle of decomposition product that covers the schists and gneisses. The greater proportion of the gold, therefore, is derived from placers which are exploited in all three colonies. Some geologists claim that they occur in two belts parallel to the coast; whether this feature has its origin in the location of the primary mineralization or in the gradients of the rivers is not clear. In some instances the river gravels grade into auriferous laterite. The laterites are well developed in the Guianas and represent the weathering products of the more basic rocks.

Jan 1, 1946

By Franklin G. Pardee

IN 1920 the Minnesota Tax Commission estimated a reserve of 1,341,674,538 long tons of iron ore in Minnesota, the Michigan State Tax Commission report showed 199,092,855 long tons in reserve in that state, and the Wisconsin Geological Survey set the Wisconsin reserves at 21,500,000 long tons. The total reserve that year for the Lake Superior District amounted to 1,562,267,393 long tons. Ten years later the reserves of iron ore in these same districts were Minnesota 1,235,227,510, Michigan 168,349,823, and Wisconsin 23,000,000, or a total of 1,426,577,333 long tons. The decrease in ore reserves in this ten-year period was 135,690,060 long tons, but the shipments were 520,746,975 long tons. In other words, the ten-year depletion in reserves was only 8.68 per cent. If similar conditions carry into the future this calculation would indicate a life for the ore reserves of the Lake Superior region of over 100 years.

Jan 1, 1933

By Henry G. Morris

The use of compressed air for the transmission of power has reached so great a development that we find numerous large establishments devoted to the manufacture of machinery for its production and application, and special periodicals published for the dissemination of information on the subject. Moreover, its employment is so general in mining operations that no apology is needed for the presentation to the Institute of such a paper as the present. The admirable articles of Mr. E. A. Rix, published in Conzpressed Air, show a wide range in the mechanical efficiency of air-compressors, varying, under different conditions, from 15 to 60 per cent.; and it is evident that any

Jan 1, 1902

E. E. Olcott, New York City: Prof. Kemp's valuable description of the Lancaster Gap mine is in line with many other able contributions on the origin of mineral deposits that the Institute has lately brought forward. The splendid contribution that Prof.

Jan 1, 1895

By R. F. Shurtz

R. Duval (Mining Engineer, Ancien eleve de PEcole Polytechnique, Paris, France) I do not agree with the Eq. 3, reading: m =1/100- [(0.214x30.4) + (0.7B6 x0.00)] =6.5pct CaO If 0.214 and0.786 were proportions by weight, the equation would represent the well known mixtures law of the conventional arithmetics and 6. 5 pct CaO would be the correct average content. But it is not the case as the author states: "In samples consisting of single grains of mineral, those grains must, as already mentioned, be either of dolomite or magnesite. Since 78.6 pct of the deposit consists of magnesite and 21.4 pct of dolomite (excluding for present purpose the presence of other minerals), for any single grains picked at random the probability will be 0.214 that is it dolomite and0.786 that is it magnesite. In 1000 such samples the expected numbers of dolomite and mapesite grains will be 214 and 786 respectively." 0.214 and 0.786 would be proportions by weigbt under the necessary condition that all grains of dole mite and magnesite should have an identical weight. Obviously it is not the case, as the specific gravities are not the same for mapesite and dolomite and the volumes of the grains are different. Furthermore, because of these differences the conditions for a random sampling are not fulfilled and we are not authorized to state that the probabilities are, respectively, 0.214 and 0.786. The author however makes a simple application of Eq. 1: M = 1/n— ? fi x i . n Should we deduce that this relation is wrohg? Not at all, but when applying Eq. 1 you must not overlook what it actually. means. Eq. 1 gives a definition of the arithmetic mean of a total of n observed values Xi and nothing else. But the average conteht of a deposit has not the same significance. It is the ratio between the weight of concerned mineral in the deposit and the total weight of the deposit. As from 1000 particles the 214 of dolomite and the 786 of magnesite have not the same weight, the two definitions do not concur, and when applying Eq. 1 the result is an arithmetic mean of figures which has no connection with what is named average contentof a deposit. The situation is similar to the calculation of an average velocity. If a car travels a first mile over at 30 miles per hr and a second mile over at 60 miles per hr, when applying formula 1 you find as average velocity for the 2 miles: 30+60 ------- - 45 miles per hour. Many people calculate in this way and they do not realize that a mistake is involved. In fact the definition of he average velocity for the 2 miles is the quotient of the distance of 2 miles by the time (in hours) necessary for 2 miles travel, i.e.: 2 ---------- = 40 miles per hr. 1 + 1 30 60 In other words, the average volocity wanted is not the arithmetic but the harmonic average of the two velocities. The above mentioned bias in the calculation of the average contents of deposits is frequent, even in the assessments made by experienced engineers and is independant of what is named the sampling error. In order to supress the bias and to be able to use Eq. 1, you must apply a correction. An example on the subject can be found in an article by Duval et al. in the January 1955 issue of the ''Annales des Mines" (French), page 19. R. F. Schurtz (Author's Reply) Mr. Duval's position is quite correct. The proportions shown for dolomite and magnesite., respectively, of 0.214 and 0.786 are, in fact, proportions by weight uncorrected for specific gravity. In our day to day operation of producing magnesite from these mines at a very substantial rate, we do not normally make corrections for the difference between the specific gravity of dolomite and that of magnesite. If these corrections are made in Eq. 3 as shown in my article, then the numbers of grains turn out to be in proportions of 0.226 dolomite and 0.774 mapesite instead of the values actually shown in the equation. For the purposes of our work, and in view of the inherently low accuracy of the data, this correction was not deemed worthwhile making.

Jan 1, 1961

By W. C. Smith, P. J. Hickey

After a short historical background of the process evolution, this article descvibes present-day plant facilities and operating techniques utilized for high-purity bismuth production. The plant is one of the world's largest, with an annual output of some one million pounds of refined bismutlz. PREVIOUS papers1 written by staff members of Cerro de Pasco Corp. have referred briefly to the production of refined bismuth. Since the Corporation is one of the world's foremost producers of high-purity bismuth, a detailed description of the process for extracting the metal may be of general interest. Following a short historical background of the development of the actual process, this presentation will trace the progress of bismuth from its entry into the primary smelting circuits to its concentration in electrolytic lead cell slimes. Our facilities for the treatment of anode muds will be described and the extractive methods given in some detail, with particular emphasis on the techniques which result in the production of refined metal. HISTORICAL BACKGROUND Shortly after Cerro de Pasco began smelting operations at Oroya, Peru in 1922, it became apparent that the dust carried by copper converter gas contained appreciable amounts of bismuth. Although dust collection efficiency was poor prior to building of the 550-ft stack and installation of the central cottrells in 1938, a large stock of dust was accumulated during the intervening years, having the following approximate composition: Oz. per ton Ag - 11.0 Pct Sn — 0.5 Pct Pb - 49.0 Pct Zn - 6.5 Pct Bi - 2.0 Pct Insol. - 1.5 Pct Cu - 0.7 Pct Fe - 2.3 Pct Sb - 3.0 Pct S - 10.0 Pct As - 7.5 In the mid-1920's, experimental crucible melts of this dust with carbon indicated that most of the bismuth and silver, and some of the lead, could be reduced to a fairly clean bullion. Other products were a small amount of leady copper matte and a slag high in zinc, arsenic, antimony, and lead; this slag contained some tin but only small quantities of silver, bismuth, and copper. After the laboratory results had been confirmed by operation of a small reverberatory, a dust reduction furnace was constructed. The ±10 pct Bi-Pb bullion produced from this operation was stocked until 1930, when an Oroya-designed converter type furnace3 was installed for the elimination of arsenic, antimony, and some lead from the bullion. This process concentrated the bismuth from 10 to about 60 pct. By means of the bismuth process developed4 by W. C. Smith at East Chicago (1909-1914) and the discovery of a method5 for separation of lead from bismuth with chlorine gas in 1929, it became possible to begin production of refined bismuth. Unfortunately, bismuth deleaded with chlorine always contained residual chlorides, and the removal of the chlorides by caustic soda left a lead content of 0.02 to 0.04 pct. This final problem was solved6 by substitution of air-blowing for the caustic treatment, which effectively removed all excess chlorine and gave bismuth which was practically lead-free. In 1934, a pilot electrolytic lead refinery began operations at Oroya. Lead smelting was resumed in 1935 and two years later a 100-ton-per-day lead refinery was put into service. In conjunction with the latter, the present-day Anode Residue Plant was constructed. Until 1940, the plant treated both lead anode slimes and dust reduction bullion. The dust reduction furnace was shut down in that year, and all cottrell dusts (with the exception of the product from the arsenic cottrell) were mixed with pyrite and treated in a Wedge roaster to eliminate all possible arsenic. Calcine from this operation joined the sinter plant feed; hence the bismuth from the copper and lead circuits was collected in the lead bullion and subsequently in lead anode slimes from the electrolytic lead refinery. The latter source has been the only bismuth-bearing material of any consequence entering the Anode Residue Plant from late 1940 to the present. A copper refinery began operating in 1948, and the cell mud from this plant is mixed with lead slimes and processed through the same circuit, though only a small quantity of bismuth is present in electrolytic copper cell residues. BISMUTH INTAKE Present-day routes which are followed by the new bismuth feed from its entry into the primary smelting circuits to its arrival at the Anode Residue Plant are traced schematically in Fig. 1. As illus-

Jan 1, 1962