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By C. M. Brinckerhoff

Safety work in mining at the Andes Copper Mining Company, Potrerillos, Chile, is divided into three parts: (1) accident prevention, (2) fire prevention and protection, and (3) silicosis prevention and control. In the company's operations a steady campaign has been waged to reduce accidents and silicosis, and to prevent fires. In the following pages the safety record for the past twelve years will be examined and the methods explained by which the accident rate was reduced. Table 1 contains yearly data pertaining to the scale of the mining operations and the accident record. Block caving is used for all ore production and the tonnage mined has aver- aged 30,000 short tons per day for the past seven years. Table 2 classifies 44 fatal accidents which have occurred since 1935. The leading causes of accidental death are transportation of ore and use of explosives, followed in order by per- sons falling, falls of ground, and by asphyxiation. In the case of serious accidents, however, the greatest cause is falls of ground, followed, in turn, by ore

Jan 1, 1949

By S. H. Ash

IN no part of the world other than a small area in Pennsylvania is anthracite mining an industry of major magnitude. As the deposits of anthracite in the United States are limited virtually to Pennsylvania, the difficulties of this industry have been commonly considered a state rather than a national problem. However, there is also national interest in the conservation and wise utilization of all the country's fuel resources and in the control of interstate waterways. The anthracite industry is confronted with a serious problem of water accumulation in many of the mines, a problem that must be solved in the near future if progressively higher mining costs are to be avoided. It cannot be solved by the operating companies without state or Federal aid, or both, owing to the magnitude of the work required, the diversity of interests of the coal and surface ownerships, the hazard to the whole mining community, and interests affected outside the mining region. 'The costs of abating the ever-increasing surface seepage to mine workings and of handling this seepage once it has occurred are beyond the eco¬nomic resources of the operating managements.

Jan 1, 1941

By E. C. Bohlen, H. l. Burghoff

THE work reported in this paper was carried out to supplement the existing information concerning directional properties and recrystallization textures of annealed brass sheet and strip. These characteristics are of direct interest when the forming and drawing properties of such material are being considered. Among those who have made contributions in this field are Bass and Glocker;1 Bauer, Göler and Sachs;2 Phillips and Samans;3 Pratt;4 Price;5 Cook;6 Richards;7 Brick;8 and Brick and Williamson.9 These investigators have found, in general, that in brass strip that shows directional variations in properties, tensile strength has a minimum value and elongation has a maximum value at 45° to the rolling direction. The most pronounced directional properties have been found in material given the greatest reductions in rolling followed by high annealing temperatures. Recrystallization texture of brass has been variously reported as (113)[112], (001)[100], and a combination of (110)[115] and traces of the primary rolling texture, (110)[112]. The directional studies have been very informative, but actual tests appear to have been confined to material in its final condition. Tests at intermediate stages have received little attention although previous history of some materials has been partly considered. Perhaps the most comprehensive investigation was made by Cook,6 who studied the directional properties of 70-30 brass strip for which the final and penultimate, or next to the last, anneals and the final reductions were varied. He found that, for any given combination of penultimate anneal and final reduction, the tendency toward the development of directional properties was reduced as the temperature of the final anneal was decreased. In addition to drawing cups and making tensile tests of the finished material at various angles to the rolling direction, he measured the frequency and the angles of twins in grains for several specimens. Plots of his twin counts showed directionality for the materials that produced eared cups. TEST MATERIALS AND EQUIPMENT For this investigation, one commercial heat of 68-32 brass was cast in the form of bars for cold-rolling, 13 ½ in. wide and 1 ½ in. thick. The analysis was as follows: 68.83 per cent copper, 0.04 per cent lead, 0.01 per cent iron, 31.12 per cent zinc (by difference). The bars were so processed to the final thickness, 0.020 in., as to obtain on this thickness all possible combinations of the variables listed below except those involving the sequence of 84 per cent penultimate reduction and 84 per cent final reduction: I. Penultimate reductions of 37 per cent, 50 per cent and 84 per cent; 2. Penultimate anneals at 800°, 900°, 1050° and 1200°F.; 3. Final reductions of 37 per cent, 50 per cent, 69 per cent and 84 per cent;

Jan 1, 1942

By C. S. Matthews, J. L. Mahaffey, W. M. Rutherford

This paper gives results of an experimental study of the sweep efficiency of a miscible displacement in a five-spot. The study was carried out in a parallel-plate glass model in which effects of diffusion were scaled at or near the molecular diffusion level. The experiments show that very early breakthrough (25 to 35 per cent of pore volume (PV) injected) may be expected in miscible floods because of the unfavorable viscosity ratio. However after 1 PV of displacing fluid is injected, the sweep rises to a reasonable value (50 to 60 per cent). Photographs show that small slugs of less than 10 per cent of PV tend to dissipate before breakthrough. A minimum slug size of 15 per cent of PV would appear to be necessary even in a relatively homogeneous formation. Presence of a slug whose viscosity is inter-mediate between that of oil and gas increases the sweep efficiency of the oil-gas system. In a typical system the sweep at breakthrough rose from 26 to 37 per cent of PV for a 25 per cent slug. The increase in sweep brought about by use of a large slug could well pay for the extra deferment cost of the additional slug material. INTRODUCTION Most miscible displacement processes involve the displacement of oil with fluids of much lower viscosity and density. The displacement process at these adverse viscosity and density ratios is dominated by instability phenomena, i.e., viscous fingers and gravity tongues. These phenomena have highly adverse effects on oil recovery. Although a number of laboratory studies have been made to determine the effect of adverse viscosity ratios on five-spot sweep patterns,l,2 the scaling of diffusion effects is uncertain. In the series of scaled model studies reported herein, an attempt was made to scale diffusion. Model studies of miscible displacements in which molecular diffusion predominates are per-mitted by controlling the parallel plate spacing which reduces convective mixing to arbitrarily small levels. To decide how this scaling relates to any particular Geld displacement necessitates an estimation of diffusion effects for the natural rock being considered and conditions under which displacement will be conducted. The approach normally taken is to extrapolate data obtained from stable miscible displacements performed in the laboratory, such as those presented by Brigham et al.3 The validity with which such an extrapolation can be applied to an unstable flow system has yet to be established. If this approach is accepted, a family of oil recovery curves can be generated for a single viscosity ratio based on Brigham's observation that the magnitude of the dispersion coefficient is dependent, among other things, upon specific rock properties. Objective of our test was to define the lower limit of this range by presenting the case where dispersion effects were reduced to the molecular diffusion level in both the transverse and longitudinal directions.

Jan 1, 1967

By Alden Greninger

TWINNED metal crystals are usually designated as either deformation twins or annealing twins. If twins are to be classified according to the treatment the metal has undergone just prior to the obser vation of the twins, there are two other possible groups: (1) solidification twins,? when observed in the as-solidified or as-cast condition, and (2) transformation twins, ? when observed in a metal which has been cooled from above an allotropic transformation temperature. McKeehan has demonstrated that ferrite does, occasionally at least, contain twinned structures2. The twins, which he studied by optical methods, were obtained during the preparation of iron single crystals by very slow cooling through A3. He proved that the twin relation was actually that which previous investigators had predicted; namely, twinning along three planes of the form {112}. Since McKeehan's discovery, little or no attention has-been given to this transformation twinning of alpha iron, or to the possibility that it might occur at all speeds of cooling from above A3 instead of merely during the prepara-tion of single crystals. McKeehan's twins were evidently regarded as interesting only in proving that a body-centered cubic metal could form twinned structures-at least under certain conditions. It is generally believed that iron seldom if ever forms annealing twins. Certainly the straight-line banding which is so abundant in annealed face-centered cubic metals is characteristically absent in iron annealed below A3. However, O'Neill3. has studied "twin-like" crystals in annealed alpha iron and concludes that the specimen he studied actually

Jan 1, 1936

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By R. HAYDEN, H. B. HALLOWELL, H. O. Hofman

THE object of refining copper in the reverberatory furnace is to obtain a metal which will have the highest attainable degree of malleability, ductility and electric conductivity, and present at the same time a level surface when it solidifies in the mold after casting. These desirable physical properties are governed by the character of the impurities and the forms in which they are present, by the amount of cuprous oxide retained by the copper, by the quantity of gas held in solid solution, by the casting-temperature, and by the thickness of the casting. The effects of impurities, of cuprous oxide and of gases upon the mechanical properties of copper have been studied by Hampe in his classical paper "Contributions to the Metallurgy of Copper." The most recent research into the effect of metals upon the electrical conductivity of copper is that of Addicks.2 The influence of cuprous oxide upon the electrical conductivity has been investigated by Walker' and Addicks.4 The absorption of gases has received' attention by Hampe,5 Stahl 6 and Heyn.7 The effects of casting-temperature have been noted by Stahl.8

Mar 1, 1907

By R. A. Nadler and

Specimens of Ti-155A (Ti-5Al-1.3Fe-1.3Cr-1.2Mo), Ti-6Al-4V and Ti-4Al-3Mo-1V were hydrogenated, aged to high strength levels, and subjected to notched stress-rupture tests and tensile tests at two strain rates. Both Ti-6Al-4V and Ti-155A were relatively unaffected by hydrogen in amounts exceeding those found in commercially -produced material. Inconsistencies in the data and a relatively low initial level of ductility prevented an accurate determination of the hydrogen tolerance for aged Ti-4Al-3Mo-1V, but there was no evidence that this alloy was any more susceptible to hydrogen embrittlement than Ti-155A and Ti-6A1-4V. THE metallurgical literature has been considerably enriched in the past five years by the publication of the results of many investigations which were concerned with the effects of hydrogen on titanium and its alloys. Although it is not the authors' intention to provide a complete literature survey of this vast field, it is worthwhile to summarize briefly some of the important factors which influence the embrittling phenomenon in a - B alloys. Some of the influencing factors are those of strain rate, temperature, and composition. Hydrogen embrittlement in a - B titanium alloys is now believed to be a strain-induced phenomenon, and whether or not embrittlement occurs at high hydrogen levels depends largely upon whether sufficient time is available for hydride precipitation. This condition is fulfilled by tensile testing at very slow strain rates or by rupture testing smooth or, preferably, notched specimens over relatively long periods. Conveniently, maximum embrittlement occurs at or near room temperature. The presence B - stabilizing elements, in amounts sufficiently small to prevent an all -B or nearly all -P condition, promotes hydrogen embrittlement and this tendency is believed to be related to the amount of a - B interfacial area present. Aluminum, by increasing the solubility of hydrogen in A titanium, greatly reduces the danger of hydrogen embrittlement, while oxygen has been shown to have detrimental effects.' The preceding discussion is based on experimental work performed on annealed a - P alloys. This early work has shown that annealed Ti-6A1-4V and Ti-155A are relatively insensitive to the embrittling effects of hydrogen.' Although no work has been reported on annealed Ti-4A1-3Mo-lV, the alloy would be expected to exhibit somewhat the same insensitiv-ity as Ti-155A. In sharp contrast to the voluminous literature on annealed titanium alloys is the paucity of reported investigations on materials receiving commercial heat-treatment cycles. To date, the most notable contributions in this field have arisen from two separate investigations on Ti-3Mn-1Fe-1Cr-1V-lMo, the so-called 3Mn comple~. These investigations

Jan 1, 1961

By William L. Boyd, Eugene L. McCarthy, Laurance S. Reid

Proper control of the moisture content of natural gas is essential to reliable operation of gas transmission and distribution facilities serving northern markets. The moisture content of natural gas is usually determined by dew point measurement at the existing pressure. For any gas of constant moistrire content. the dew Point varies with the pressure. A correlation of the data of several investigators is prezented in graphical form by the authors. These data were correlated by the authors and F. M. Townsend, C. C. Tsao. M. I). Rogers. Jr.. and J. A. Porter. graduate students in chemi(.a1 engineering at the University of Oklahoma. Of articular interest are the hitherto unpublished low temperature data observed by Wickliffe Skinner. Jr., which are included in this correlation. PRESENTATION OF DATA The problem of interpreting water dew points, or saturation temperatures. of natural gas in terms of specific moisture con-tent has increased in importance during the past decade bec.arl.;e of extensive development.; in the transmission and petro-chemical phases of the natural gas industry. Virtually all gas transported to northern and eastern markets must be dehydrated to a low water vapor content to prevent hydrate formation in transmission and distribution lines and resultant interruption.; in gas deliveries. Complete dehydration is required in certain phases of tile petro-chemical industry involving low-temperature operations. It is a well-known fact that the water vapor content of pure hydrocarbon vapors and their mixtures at superatmospheric pressures cannot be predicted with accuracy by assuming validity of the ideal gas laws." Earlier interest in the general problem was concentrated on the water vapor content of pure hydrocarhons and hydrocarbon mixtures in the pressure and temperature ranges common to gas and oil producing reservoirs in order to obtain fundamental data for the improvement of production techniques and the furtherance of reservoir studies. Excellent data are published for pressures ranging from atmospheric to 10,000 psig and for temperatures ranging from 100° to 460° F4,9,10,11 and are found to be in close agreement. However, experimental data at high pressures and temperatures below 100°F are comparatively limited in scope. Experimental data in the lower temperature range have been reported by Laulhere and Briscoe.8 Deaton, et al,2,3 Hammerscllmidt,5,6 and wade," In general, the pressures employed in these investigations ranged from atmospheric to 1.000 psig while temperatures ranged from 32° to 120°F; i.e., the usual conditions encountered in gas transmission line operations, Additional data were reported by Russell, et al,12 at pressures as high as 2.000 psig and covering a rather narrow atmospheric temperature range. In 1947, Hammerschmidt published a correlation of all available data,' in which the water vapor content of gases at saturation. under high pressure and low temperature. was predicted by extrapolation. In 1948, Wickliffe Skinner. Jr.. presented data on the moisture content of a low nitrogen content gas at low temperature and at pressures ranging upward to 1.500 psia.1-3 Comparison of Skinner's experimental data with the extrapolated data of Hammerscllmidt revealed an appreciable variation in the lower temperature range. emphasizing the need for a new correlation which would rely on Skinner's data at lower temperatures. Careful scrutiny of available data suggested that presence of an appreciable quantity of nitrogen in a gas mixture may affect its saturated moisture content so that data obtained from gases with more than three per cent nitrogen were not used in this correlation. CORRELATION OF DATA Data employed in this correlation are presented in Table I. The data of Dodson and Standing.4 McKetta and Katz,9 and Olds, Sage and Lacey10 were compared and found to be in close agreement so that the data of Olds. et al, re-plotted in a more convenient form by the Humble Oil and Refining Co.,' were used for temperatures of 100°F and above. Skinner's data were used for temperatures below 40°F. Between these intermediate temperature limits, the data of Hammerschmidt.7 Wade" and extrapolated data of Olds. et al.1 were tabulated

Jan 1, 1950

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,' and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson' determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12'13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By R. S. Busk

Niels Engel (University of Alabama, University, Ala.)— In this paper it was pointed out that the electron-gas and energy-band theory accounts for the fact that the lattice parameters exhibit a sudden change when the electron concentration (number of bonding electrons per atom) exceeds a certain number around two. This statement is said to support and prove the electron-gas theory. But this theory is not able to account for a series of experimental data. Also several expectations, deduced from this theory, are not found to exist. In Figs. 6 and 7 the energy bands of the second and third periods are given as they must be assumed in order to account for the electrical properties of the elements in these periods. In Figs. 6 and 7 the electron-gas and energy-band theory is compared with the electron-oscillator hypothesis in accounting for the properties of the elements in the second and third periods. Fig. 6 shows the second period, The energy-bands are overlapping and separated to be in agreement with the electrical conductivity of the elements. The oscillator hypothesis explains conductivity due to electron vacancies. In graphite there is a closed s-shell in every other atom and two vacancies in the others. Conductivity is therefore only maintained by migration of s-electrons in graphite. In boron there are no s-electrons. The diatomic molecules of nitrogen and oxygen and the paramagnetism of oxygen can be accounted for by a similar behavior as the s-electrons of the bonding electrons. But this explanation will deviate too much for the purpose of this discussion. Fig. 7 shows the third period. In the energy-band picture about two s-electrons are assumed in magnesium and aluminum, but only one s-electron is assumed in silicon. The diamond lattice is assumed to be controlled by a sp3 hybrid. However the electron distribution develops ideally according to the oscillator hypothesis. Only sodium, magnesium, and aluminum exhibit electron vacancies and conductivity. To account for the insulator properties in Si, P, and S in the third period it must be assumed that the four last added p-electrons must be taken up in bands containing only one electron per band.' (Compare the electron band picture in Hume-Rothery.' Hume-Rothery does not consider the insulator properties of the nonmetals.) In the second period already the first p-electron must have entered a single electron band. Based on the energy-band picture in Figs. 6 and 7, the following questions must be asked: 1—Is it consistent with the energy-band idea that electrons of the same kind (p-electrons) can be divided into separated bands? 2—Is it consistent with the energy band idea that single electron bands can exist? 3—Why are the first two p-electrons (in boron and diamond) separated into two single electron bands in the second period, but overlapping in the third period (aluminum)? 4—Why are s-electrons and d-electrons taken up in continuous overlapping bands, while p-electrons are divided into single electron bands? 5—Why do the peaks and valleys (y and w and further x and z) of the energy band below four electrons per atom not show up in the electrical conductivity of alloys? For example consider the Li-Mg system or the alloys between Mg and three electron metals where the mentioned discontinuity in the lattice parameter is found. 6—Why does the beginning of the p-electron band (x) not show up in the lattice constants similar to the filling up of the s-electron band (z) ? In magnesium alloys the electron-gas theory postulates the first Brillouin zone to be filled at about two electrons per atom. This is claimed to explain the sudden change in lattice spacing and c/a values of several magnesium alloys when the electron concentration exceeds a few percentage points over two electrans per atom. This was emphasized in the paper by Busk. If the electron-gas energy-band theory is correct a sudden change in electrical conductivity and possibly other properties .should be expected when the same electron-concentration or temperature is exceeded. A sudden change in lattice spacing or other properties should also be expected when the filling degree is such that p-electrons are introduced into the p-band, for example at x in Figs. 6 and 7. Such phenomena are at found by experiment. and If the number of electrons should vary with the energy level depending on the average number of bonding electrons per atom, the electrical conductivity should be expected to vary in accordance with the energy band layout (Figs. 6 and 7) caused by different numbers of conducting electrons at different filling up degrees. Nothing indicating such a behavior is observed. In addition to these discrepancies between the electron-gas and energy-band theory and measured data, the theory violates the principles developed along with the Bohr theory of atomic structure. According to these principles a filled shell is saturated and therefore unable to form bonds. Therefore two S-electrons per atom should form a closed or saturated shell, which has been pointed out as accounting for the inability of helium to form bonds. Beryllium, magnesium, or calcium atoms with two s-electrons should be expected to form inert atoms with properties almost like the helium atoms. Several other inconsistencies and disagreements with measured data of the energy-band theory can be mentioned. Some of these are discussed with reference to other papers. 8 Because the electron-gas and energy-band theory seems to fail on several points, I have developed another theory which can account for all the phenomena the electron-gas theory is able to account for. This new theory is further able to account for things which are impossible to explain by the electron-gas theory at the present state.

Jan 1, 1953

By Robert S. Archer

THE proper material of construction for a given purpose is that material which meets the requirements satisfactorily at the lowest ultirnatc cost. It is consistent with this principle that most aluminum castings are made of an alloy containing about 8 per cent. copper. This alloy possesses mechanical properties satisfactory for general engineering purposes together with manufacturing characteristics leading to the production of finished castings at low cost. It is to the aluminum industry what gray iron is to the iron and steel industry. Just as some services require "semi-steel," malleable castings or steel castings instead of gray iron, there is a certain and growing demand for aluminum castings of superior strength or ductility, or both. Since the beginning of .the industry producers and others have sought to develop alloys or processes by which such castings could be made. Out of these efforts have emerged many alloy compositions and special processes, of which only a few have had sufficient merit to survive. It is the purpose of this paper to describe those which seem to the authors to offer the greatest promise for the production on a commercial scale of aluminum castings of superior mechanical properties, with special reference to heat-treated castings. The suitability of an alloy or process for actual manufacture is affected by so many factors that the problem of appraisal is not a simple one. Since this is such an important part of the whole subject it is proposed to discuss briefly some of the requirements. The final verdict is of course the result of commercial trial and experience. It will therefore, perhaps, be profitable to employ a somewhat historical method of treatment in discussing the subject of alloy development. The alloys or processes to be used in the production of aluminum castings are to be considered from the standpoint of their effects on both the utility and the cost of the finished casting. Specific gravity and mechanical properties come under the first head, while the properties

Jan 1, 1927

By J. A. Morgan, R. E. Lund, D. E. Warnes

The design, operation, and performance of an integrated pilot plant for recovering zinc and copper from a complex sulfide ore are described. Metallurqical processing comprised selective sulfate roasting in a fluid bed, leaching in a weak sulfuric acid solution, recovering copper by cementation with scrap iron, air oxidation to remove soluble iron, more-or-less conventional Purification for removal of impurities deleterious to zinc electrolysis, recovering zinc by electrolyzing solutions, and recycling spent electrolyte to the sulfating roaster. The effects of several feed preparation and roasting variables on the sulfation response of zinc, copper, and iron are set forth, together with the electrolyzing characteristics of the zinc solutions. SEVERAL years ago, St. Joseph Lead Co. undertook a research program to develop procedures for winning values from a complex ore. The deposit was a massive sulfide ore body containing upwards of 65 pct pyrite. Gangue, composed principally of quartz, calcite, dolomite, and alumina, comprised only 10 to 20 pct of the mineralized zones. Zinc, lead, and copper values were variable, but averaged about 6.7 pct Zn, 2.6 pct Pb, and 0.4 pct Cu. Early in the exploratory test work, it was established that the intimate physical association of the minerals in the ore made beneficiation by conventional flotation procedures difficult. Accordingly, in addition to a comprehensive program to investigate physical methods of ore beneficiation, a research program was established to develop a direct metallurgical method for processing the ore. After surveying a number of potential methods for recovery of both metal and sulfur values, effort was concentrated on the development of a sulfate roasting process. It is the pilot-plant development of the sulfate roasting-solution purification—electrolyzing procedures which forms the subject of the present paper. PREPILOT PLANT INVESTIGATIONS From a thermodynamic viewpoint, it is feasible to sulfate selectively a host of metals, including Zn, Cu, Pb, Cd, Ni, and Co, in an iron sulfide ore without sulfating iron. Of course, a number of conditions such as roasting temperature and gas composition must be controlled. In addition, as first disclosed by Hybinette,' an alkali metal salt is frequently beneficial in promoting the sulfation reactions. The application of fluid bed roasting to the sulfate roasting of nonferrous metals was pioneered by Stephens of Battelle Memorial Institute.' Subsequently, Falconbridge Nickel Mines, Ltd. developed an unique process for selectively sulfating and recovering nickel, copper, and cobalt from their nickeliferous pyrrhotite, which recently has been described in an excellent paper by Thornhill.3 One of the unique features of the Falconbridge process is that the feed is introduced into the fluidized roasting furnace in a manner such that the feed slurry is broken up into droplets and the droplets lose their moisture before contacting the surface of the fluidized bed. The dried droplets do not tend to cake or fuse, but rather remain as discrete agglomerates of concentrate particles and roast without significant degradation. St. Joseph, aware that Battelle Memorial Institute had participated in the development of the Falconbridge process, obtained permission from Falcon-

Jan 1, 1962

By R. S. Dean

IN THE COURSE of its investigations directed toward providing strategic metals from domestic sources and toward utilizing power from Federal power projects in West, the Bureau of Mines concluded some years ago that the development of a method for producing electrolytic manganese might well be an important step towards both goals. Accordingly, laboratory investigations were undertaken in 1935. Further studied on a relatively large laboratory scale indicated that electrolytic manganese could be made from domestic ores at a cost not out of line with other nonferrous metals. On the basis of these results, the Electro Manganese Corp. Operating under U.S. Patent 2,119,560 issued to S, M, Shelton and assigned to the Secretary of the Interior for administration, undertook commercial production of electrolytic manganese at Knoxville, Tenn, This company has brought the process through the pilot-plant stage successfully, and is now regularly producing approximately one ton a day.

Jan 1, 1941

By I. R. Kramer

The stress associated with the high-dislocation layer at the surface of deformed aluminum crystals was measured by progressively polishing the specimen and determining the change in the initial flow stress when the specimen was reloaded. This surface stress increased linearly with strain in the Stage II and Stage III region. The depth to which the high-dislocation layer extends was found to be 0.0025 in. The influence of the surface layer on Stage I is discussed and it is shown that Stage I ends when, on the secondary slip system, the difference between the applied stress and the opposing stress due to the surface layer is equal to the critical resolved shear stress. In previous papers'-3 it was shown that the surface exerts a pronounced effect on the plastic-flow characteristics of metals. For fcc metals it was possible to increase the extent and decrease the slope of Stages I and II and decrease the work-hardening coefficient of Stage II by removing the surface of the specimen continuously during the deformation process.2,3 More recently,L it was shown that the activation energy for plastic deformation and the activated volume were also influenced by the surface. These changes were related to the existence of a high concentration of dislocations in the region near the surface of the deformed specimen and it was concluded' that the effective stress, T, acting on a dislocation was T = Ta-Ti-Ts [1] where 7, is the applied shear stress, Tj is the internal stress, and TS is the stress associated with the surface region containing the high concentration of dislocations. From Eq. [I] it is seen that the effective stress, 7, acting on a dislocation is a function of 7,. Therefore 7, becomes important in any description of the work-hardened state. In this paper the value of 7, as a function of strain and its variation with depth are reported for aluminum single crystals. In particular, it will be shown that the end of Stage I occurs when the net stress, 7, on the secondary slip system is equal to the critical resolved shear stress. To measure Ts, single crystals of aluminum were deformed in tension to various strains, whereupon the load was removed and a known amount of metal was removed by electrolytic polishing. The differ- ence between the final flow stress before the specimen was unloaded and the initial flow stress upon reloading is designated as ?Tp and is the decrease in the stress due to the removal of the surface layer in whole or in part. The value for Tp is taken equal to -Ts. EXPERIMENT PROCEDURE The details of the tensile apparatus, method of electrolytic polishing, and crystal preparation were the same as those used previously,1"3 The single crystals were 1/8 by 1/8 in. in cross section with a 3-in. gage length. The initial purity of the aluminum was 99.997 pet. The specimens were held in vacuo at temperatures 50°C below their melting points for 16 hr and furnace-cooled. Just prior to the application of the tensile stress the specimens were electrolytically polished to remove 0.004 in. from the thickness. This latter operation was conducted after the specimen was placed in the tensile apparatus. The tensile tests were conducted at a strain rate, i, of 10"5 sec-' and a temperature of 3°C. The aluminum crystals used for the determination of 7, are designated A1-3-12 and A1-116. The orientation of the various crystals used throughout the investigation is shown in Fig. 1. The ?Tp values for specimens A1-3-12 as a function of Ax were determined mainly at four strain levels, i.e., ? = 0.0217, 0.0381, 0.0593, and 0.075, where Ax is one half of the total reduction of the thickness after polishing and ? is the re-

Jan 1, 1965

By R. R. Hart, B. C. Wonsiewicz, G. Y. Chin

In recent years there has been increased miniaturization of electromechanical devices to keep pace with current trends toward smaller electronic components. A major problem facing the designer, however, is the higher stresses encountered by the material as a result of shorter springs. Hence an improvement in the elastic limit, as approximated by the 0.01 pct offset yield strength, would be highly desirable. An increase of 25 pct in the yield strength, for example, will permit a 20 pct reduction in both the length and thickness of a cantilever-type spring while maintaining the same compliance. One technique of improving the yield strength that has received little commercial attention is crystal-lographic texture strengthening.1,2 Texture strengthening is expected to be most beneficial in materials of hcp structure, but considerable gain can also be expected in cubic materials. A wire with a (111) fiber texture, for example, is expected to be 20 pct stronger than randomly oriented material, and 50 pct stronger than wire with a (100) fiber texture.293 For sheet specimens with a {110}(112) texture, characteristic of many heavily rolled fcc alloys, the (111) transverse direction is expected to be the maximum yield strength direction, about 20 pct higher than that in the (112) rolling direction.' In addition, the (111) direction is the direction of maximum modulus of elasticity for most cubic alloys. A large value of the elastic modulus could be desirable in designs where stiffer springs are required. To test the above idea, a 0.090 in. (-2.3 mm) thick commercial grade A (5 pct Sn) phosphor bronze sheet, a widely-used material for relay springs, was rolled from the spring-tempered condition (60.5 pct reduction) to various additional reductions up to a total reduction of 95 pct. Subsequently, additional material was obtained with a total thickness reduction of 97.3 pct Standard tensile specimens were prepared from the sheet material with the tensile axis parallel to and at 90 deg to the rolling direction. Tests were run on an Instron testing machine at a strain rate of about 0.050 min-l. Textures were determined by the use of the reflection pole-figure technique. Data were obtained using nickel-filtered CuKa radiation and with the aid of a Siemens pole figure goniometer. The X-ray pole figure studies show an incrzasing development of the texture toward the {110}(112) ideal

Jan 1, 1970

By E. T. Turkdogan

The activities of SiO2, FeO, and Fe2O3 are calculated from previous experimental data on the activity of oxygen in Fe-Si-O melts at 1550°C. Using the oxide-activity data, the free energy of formation of fayalite from its oxides is evaluated for 1550°C. A number of investigators1-4 contributed to the study of the state of oxidation of iron in SiO,-FeO-Fe,O3 melts and the phase equilibria in the system Fe-Si-O. In a more detailed study, Schuhmann and Ensio5 and Michal and Schuhmann% easured the state of equilibrium in the SiO,-FeO-Fe,O3 melts saturated with y-iron or silica or both under low-oxygen potentials and within the temperature range 1250" to 1350°C. Similar measurements were also made by Turkdogan and Bills7,' over wide ranges of composition and oxygen potentials at 1550"C. Using the experimental data on the oxygen activities in the ternary system, Schuhmann' calculated the activities of silica and ferrous oxide in Si0,-FeO-Fe2O3 melts for 1350°C. Adequate knowledge on the activities of the constituent oxides of melts is essential in the study of reaction-equilibria and reaction-kinetics in oxide-melts. With this in view, the activities of oxides in SiO2-FeO-Fe2O3 melts at 1550°C are computed using the experimental data of Turkdogan and Bills7'8 on the oxygen activities in these melts.

Jan 1, 1962

By P. D. Hunt, B. Tani, M. G. Chasanov, R. Schablaske

The Zn-Vphase diagram was studied by thermal. metallographic, X-ray, and sampling techniques. Three ternary phase equilibria were observed: Mutual solid solubilities in vanadium and zinc appear to be negligible. The liquidus line is retrograde from 670° to 756°C. 1 HE only information in the literature relating to the Zn-V system was a study of corrosion of vanadium by liquid zinc' and an examination of the effectiveness of zinc coatings in protecting vanadium-base alloys from oxidation at high temperatures.2 Establishment of the Zn-V phase diagram was undertaken as part of a study of transition metal solubilities in liquid metal solvents. Chemical, metallographic, thermal, and X-ray diffraction analyses were used to determine the diagram. MATERIALS AND EXPERIMENTAL PROCEDURES Vanadium (99.86 pct) in the form of powder and small chips was employed. Stick zinc (99.99 pct; major impurities: 10 to 15 ppm Pb and 20 ppm Cu) was used in the liquidus determinations and thermal analyses; zinc powder (98.80 pct) was used to prepare intermediate compositions. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The apparatus and sampling techniques were similar to those described by Martin, et al.3 The entire metal sample was dissolved to preclude analytical errors due to segregation on cooling. Vanadium was determined amperometrically, using iron (11) as the titrant,4 to an estimated accuracy of 1 pct. Standard techniques of thermal analysis were employed to examine alloy specimens contained in alumina crucibles under helium. Heating and cooling rates were about 1°C per min. At least five heating and cooling cycles over the range 420° to 700°C were performed for each of two Zn-15 pct V alloys. A Zn-0.2 pct V alloy was used in the determination of the eutectic temperature. The separation of intermediate phases from zinc-rich alloys was carried out by selective leaching with ammonium nitrate solutions. For further investigation of intermediate phases 1/4 in. diam powder compacts were prepared by pressing at 80,000 psi and were annealed in argon at 415" to 450°C for 10 days. Larger quantities of intermediate phases were prepared in sealed tantalum capsules heated in a rocking furnace. Temperatures were determined to an estimated accuracy of 0.5°C with a Pt/Pt-10 pct Rh thermo-

Jan 1, 1963

By Jack C. Haptonstall

This paper describes the analytical characteristics of Western subbituminous coal and the manner in which these characteristics apply to their use in a utility-sized steam generator. It compares these characteristics with those of typical Midwestern coal and Eastern bituminous coal. The paper also reviews in detail the design considerations that must receive attention when various blends of these three coals, or any combinations thereof, are planned to be used. This research paper describes variations in analytical and utilization characteristics when coals from different origins are blended in order to achieve a predetermined sulfur content for the purpose of predicting sulfur oxides emissions as they affect environmental regulations and the resulting alterations in utilization characteristics such blending would cause, and how such blends of coal would affect a utility-sized steam generator.

Jan 1, 1979

By Roger L. Beals, George A. Tweedy

I. INTRODUCTION. THE results of the cyanide-operations, given in detail in the following paper, show the progress that is being made at the Minas del Tajo. The old pan-amalgamation process, in operation up to and including 1905, while paying a profit on high-grade ores, was no longer able to treat profitably the ores in sight at that time, hence an alteration in the process was imperative. The success of this alteration is eloquently expressed by the following data Pan- Amalgamation. Cyanidation. 1905. 1907. 1903. Tons treated, . . 51,387 53,983 69,300 Value per ton (U. S. currency),. $10.75 $8.39 $8.28 Extraction, per cent., 65.00 88.50 S7.45 Extraction, per ton. .- $7.00 $7.4.; $7.24 Total cost, per ton treated, 6.50 4.311 4.01 Profit, per ton treated, . . 0.50 3.07 3.23.;

Feb 1, 1910