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By R. Dawson Hall

WHAT are the opportunities for the services of engineers in the coal mines? The best answer perhaps can be made by detailing the present lines of development in the bituminous coal mining regions. They are just at the beginning of a period that can be conservatively termed revolutionary. A few glimpses of new possibilities in economic mining that will reduce the cost of bituminous coal at the mines by at least one half have convinced almost everyone that a change must shortly come about. The cost of housing has become such a burden, especially in mountainous regions, that development which demands the hiring of more men and constructing more houses would not be profitable. The introduction of mechanical aids to mining, transportation and dumping suggests a way of obtaining a large tonnage with the same or a smaller number of men with no further house construction. At the same time the restriction of immigration has made it increasingly difficult to obtain men inured to hard labor. Modern civilization is not productive of muscular energy and at the same time it provides men who are not indisposed to the use of the mental effort required to direct the physical forces now available for the replacement of such energy.

Jan 1, 1924

By E. Bicknese, R. Clark

The mechanism and rate of reduction of FeO at conditions similar to those in the stack of a blast furnace have been determined for temperatures from 980" to 1165°C. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal in a static system (no flow of reducing gas) have shown that the CO2-CO ratio of the product gas depends upon the relative reactivities of the Fe2O3 and charcoal. In a systern with a "hot blast" of CO and Nz (simitar to dry bosh gas), synthetic FeO, and actiuated coconut charcoal, the rate of reduction was not sensitive to the flow of reducing gas, and the rate-controlling step alas the chemical reaction at the metal-oxide interface. Wherz solid carbon was not present, a critical flow rate of reducing- gas had to be met in order to prevent a lowering of the reduction rate. The effect of a less-reactive carbon (blast-jurnace coke) and of a "natural" FeO on the mechanistn and rate, and the mininum amount of carbon necessary in the charge to tnaintain the reducing potential of the gas phase, have been determined. THE importance of iron oxide reduction processes has encouraged many studies of the process reaction kinetics. Despite this, the mechanism is not well-understood and three main theories have evolved, which can be stated as follows: A) the rate-controlling step is diffusion, either gaseous diffusion of the reductant or product gas through a porous solid,' or solid-state diffusion of iron and oxygen atoms through the so1id.2 B) The slow step is diffusion of reducing gas through a stagnant boundary layer. C) The reaction rate is controlled by the chemical reaction occurring at the metal-oxide interface and is proportional to the area of this interface.3 By increasing the velocity of the reducing gas to a flow rate beyond which no increase in the reduction rate is observed, critical flow rate, it may be possible to eliminate B as the slow step. However, as warnere points out, the establishment of a critical flow rate may only assure that the reaction is not limited by a reduction in the reducing potential of the gas and that B may still be the rate-determining step. Edstrom and Bitsianes and Seth and Ross8 show that A and C may both be correct for the reduction of the same oxide, depending upon the stage of the reduction, and that the relative importance of the two mechanisms varies with the porosity of the oxide. Themelis9 has derived expressions which express A, B, and C in terms of the fraction reduction, Rx, of a spherical particle. Thus, in the case of A a plot of In (1 - Rx) vs time must be linear and the time to reach a given reduction is proportional to the square of the particle diameter. For B a plot of (1 - Rx) vs must be linear and the time to reach a given reduction is proportional to the square of the diameter. For C a plot of 1 - (1 - RX)1/3 vs f must be linear and the time to reach a given degree of reduction should be proportional to the diameter. In the case of mixad controlled reactions, none of the plots are linear over their entire length. The results of previous studies, in which the rates of gaseous reduction of iron oxide were measured in the absence of carbon, may not correspond to blastfurnace practice because they ignore the effects of the Boudouard reaction. CO2 +C — 2CO The presence of carbon may alter the mechanism or the rate of iron oxide reduction through an enrichment of the gas phase by Eq. [1]. In this case, the presence of and reactivity of carbon become important. If the Boudouard reaction has no effect on the rate of reduction, the reducing gas could be supplied by some means other than the gasification of carbon at the tuyeres and carbon could, theoretically, be eliminated from the burden. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal were made to determine if the reactivity (surface area) of the Fe2O3 had any effect on the product gas composition. Two size fractions of Fe2O3 were reduced with charcoal in a static system (no flow of reducing gas). In each case the charcoal was -100 + 325 mesh and was 25 pct of the total charge. One fraction of the reagent-grade Fe2O3 was submicron in diameter. The other fraction was -100 + 200 mesh and was prepared from the former by compacting, sintering at 1300°C, crushing, and screening. In each experiment, the reaction vessel was filled with a mixture of CO and CO, which would be in equilibrium with FeO and iron at the reaction temperature. A furnace was heated to the desired temperature, the vessel was placed in the furnace, and the gaseous products of the reaction were collected and analyzed. The results of these experiments, Fig. 1, show that the gas phase associated with the submicron oxide is more oxidizing than that with the -100 + 200 mesh oxide. Therefore, in a static system, the relative rates of the reduction reaction and the gasification of carbon depend upon the reactivities of the Fe2O3 and charcoal. The reduction of FeO to iron is the most important reaction occurring in the blast furnace and is probably the slowest of the several reduction steps. The mechanism and rate of reduction of FeO in a system containing carbon and a flow of dry bosh gas have been studied. TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AlME

Jan 1, 1967

By D. J. Weintritt, R. G. Hughes

Statistics show arz increase in the average depth of wells drilled in recent years. As a corollary to this trend, drilling fluids have been improved in an effort to meet the problems inherent at temperatures approaching 500°F. Of importance are (1) deterioration of mud components and (2) the effect of solids on filtration and rheological properties. High-temperature, stable water-base and oil-bare muds are discussed. Those areas in which differences exist are pointed out. Results are based on data taken from the Fann consistotneter, rheometer and shear-strength measurements, static and dynamic filtration tests, methy-lene blue test for bentonite solids and specific heat measLrrenlents of muds. INTRODUCTION Higher well temperatures go along with the fact that the average depth of wells continues to increase. Recent data by Gardner' lists 137 completions deeper than 15,000 ft for the first half of 1964 with a record second-half total of 167 wells drilling or proposed. In addition, there has been an increase in drilling for steam for power production or mineral recovery. In this application the depths are modest, but the mud may approach the critical pressure and temperature of water. Scearce and Magnon' report drilling mud used at temperatures of about 700°F in the Salton Sea area of California. Most deep wells have been drilled with water-base muds. In recent years, however, there has been a substantial increase in the use of oil-base muds because of technological advances in effective additives. The significance of this development was dealt with in considerable detail by Simpson and his co-workers.3 Additiona1 field data have now been obtained to indicate that oil muds are competitive in control, performance and cost with the best types of water muds for use at high temperaturc. This parallel offer of two very different fluid systems, each offering a similar variability in performance, cost and convenience, has created the need to evaluate the merits of these fluids under specified conditions so that the advantages and disadvantages of each can be weighed in relation to the over-all drilling program. This paper is not intended as a review of all the factors. Rather, it attempts to emphasize: (1) important condltions and facts peculiar to high-temperature drilling muds, (2) that more than one imposed test condition or testing method is necessary to describe the quality of a mud at high temperature and (3) that elaborate experimental precautions are necessary whenever laboratory data are used in selection of a mud for field use. WHAT IS A HIGH-TEMPERATURE DRILLING FLUID? For the purpose of this discussion, a high-temperature drilling fluid is any system so formulated or treated to economically minimize the effects of temperature on the properties of the fluid. Our experience in drilling fluids suggests that these effects become obvious for many mud materials at temperatures of 300F or higher. It is understood that hydrolysis of starches, depoly-merization of certain organic thinners, or irreversible chemical reactions (such as that of clay and lime) can affect filtration, viscosity and shear strength at less than 300F. However, the temperature level is not a serious point and in no way affects the precautions and techniques used in this study. An up-to-date review of the literature on high-temperature drilling fluids and the many variations was treated by Rogers'in 1963. EXPERIMENTAL REQUIREMENTS TESTING EQUIPMENT AND PROCEDURES With the advent of deeper drilling and increased demand for temperature-stable drilling fluids, new testing equipment and laboratory techniques were devised for the evaluation of drilling fluids subjected to elevated temperature and pressure. While the equipment has not been standardized, it is in widespread use. Milligan et al. Qescribe a filtration cell for determining the filtration properties of drilling fluids at temperatures in excess of 300F. They showed the effect of variations in temperature and pressure on oil and water muds filtered in the 300 to 400F range. The dynamic filtration apparatus described by Simpson6 permits the study of the filtration properties to temperatures of 350F for drilling fluids circulated over sandstone cores. Watkins et al.' describe the use of pressure bombs for studying the effect of prolonged periods of elevated temperature upon the gelation or solidification of drilling fluids. Chisholm et a1.' describe the use of a modified cement consistometer adapted for use in drilling fluid evaluations. A similar consistometer is used in this study, although the application and data-recording method have been changed. The consistency of a mud sample is measured by timing the movement of a soft iron bob which is magnetically moved up and down in the sample container.* Changer in the time of travel and the temperature of the mud at that moment are plotted with a two-point Brown Elec-tronik Recorder. A 10-in. chart with a speed of 4-in./hr is used. Fia.- 1 is a generalized internretation of the data ob-

Jan 1, 1966

By Nathaniel Arbiter, Norman L. Weiss

Factors now accelerating the trend to larger concentrators and larger equipment units are reviewed. After almost 40 years of stability with unit sizes less than 100 cu ft, 200 and 300-cu-ft flotation-cell units are now operating and a 500-cu-ft machine is being built. The design of these cells is considered, as is the design and operation of flotation circuits against the background of the need to achieve greater process efficiency while holding down operating and investment costs. Particular attention is paid to the scale-up problem. With the newer cells having five to ten times higher unit capacities, the advantages resulting from this in sampling, mill operation nnd control, testing and plant layout are indicated, as well as the broad direction for changes in the overall design of 50,000 to 100,000-tpd concentrators. A comparison is given of the available larger cells of U.S. manufacture with analysis of differences and similarities. After almost 60 years of application in this country, froth flotation is still by far the most important process for concentrating metallic ores as well as a number of nonmetallic ores including fluorspar, phosphate rock, and potash. Its use on iron ores and coal is increasing. In the metals groups, the largest plants and the greatest progress are found in copper and molybdenum mills, and the section of this paper that deals with applications will be found most pertinent to that field. During its long reign, the flotation process has passed through several phases of evolution and has achieved progress in economy, efficiency. and simplicity of operation. Much of today's success in the flotation of low-grade ores can be attributed to that progress. Even more important to us than our ability to cope with today's conditions are tomorrow's problems, which we can contemplate with some prescience and confidence. Our annual production of copper, lead, zinc, and molybdenum—to mention only the most important metals occurring in the U.S. as sulfides- must be held at a high level in the face of a declining grade of ore. It is probable that the tonnage of such ores mined and processed will double in this country before the turn of the century. Not only will many of the existing flotation mills be enlarged again and again, but larger mills will be built here and abroad to meet our needs. At this moment, in fact, there are at least three proposed new foreign mills or expansions that envision 100,000-tpd milling rate on copper ores. Table 1' shows the trend in copper ore grades in U.S. in recent years. Table 2' shows the projected annual growth rate of consumption 1966-1985. A study by one of the authors 25 years ago showed that of 32 copper mills in North America with more than 100-tpd capacity, only eight had capacities exceeding 10,000 tpd. The average for these eight was 25,000 tpd. These included the three giants of that day, Magna, Arthur, and Morenci; the other five averaged a little over 10,000 tpd. Today instead of the eight mills with capacities exceeding 10,000-tpd capacity we have 25, and the mill with less than 1000-tpd capacity is fast becoming extinct. Much less range is found in lead and zinc mills, which are still generally small except for the few with over 1000-tpd capacity in Missouri, Utah, and Idaho, and a few zinc ore mills in the same size category. Molybdenum and potash operations are the fastest growers in North America today, but when one considers the projected increase in consumption of copper together with the projected decrease in grade of ore (3% annually), he can foresee that copper ore milling will soon lead the list. Technological improvements to meet the challenge of lower-grade ores have taken the wholly predictable path toward bigger equipment. In mining, shovels, draglines, scrapers, and trucks have led the way; in ore processing, we have seen a rapid increase in size of grinding mills, flotation cells, and pumps. Twenty-five years ago, for example, the 10-ft-diam ball mills treating 2000 tpd at Morenci were considered the giants, but today some grinding mills in similar service have five times that capacity. The specific matters to be dealt with in this paper are 1) the underlying principles that affect flotation-machine design, and the conditions required to produce

Jan 1, 1971

By Wayne Loel

THE application of aerial photographs to all phases of geologic mapping is set forth, indicating the advantages to be gained in different types of country and under varying climatic conditions, Methods of field and office procedure are given from a geological point of view, as well as suggestions regarding the best methods of aerial mapping for different uses and under varying field conditions, including the study of submarine geology. Aerial photographs with accompanying geologic maps are shown to illus-trate the appearance from the air of different geologic features under varying climatic and topographic conditions.

Jan 1, 1938

By AIME AIME

THE first meeting" of the Iron and Steel Division was held Tuesday afternoon, Feb. 17, with nearly 100 men present and C. B. Murray as chairman. This was a round table discussion of iron ore beneficiation and of its relation to blast-furnace operations, and only one paper was presented, by Clyde E. Williams. Mr. Williams discussed the future of the Lake Superior district in its relation to the iron and steel industry. He stated that although estimates had shown that the total life of the present known iron ore reserves of the Lake Superior district was 20 to 30 years and that many believed that as a result of this depletion foreign ores would be brought to the Atlantic Seaboard, thus causing a displacement of the steel industry to the East, he believed that the Lake Superior district would continue to be the important producer of iron ore used in this country for decades beyond the predicted time before the exhaustion of the present known reserves. He described the three general types of ores that required concentration and pointed out the needs for research and the proper methods to be used in processes for the beneficiation of these low-grade materials. He discussed the effects of fine concentrates and the use of agglomerated ores in the blast furnace. This general summary led to interesting and valuable discussion on the various economic, ore-dressing, and blast-furnace problems in large-scale development of beneficiation. Perry Harrison described recent developments in sintering and the properties of iron ore sinter. T. B. Counselman and W. H. Coghill discussed the merits of classification of iron ore previous to tabling. Robert Faulkner and J. E. Little described the beneficiation plant of the Bethlehem Steel Corporation.

Jan 1, 1931

By B. H. Caudle, W. J. Bernard

Factors which influence the success or failure of a waterflood can seldom be determined in the laboratory. For this reason pilot waterfloods are initiated in a repreventative portion of the oil reservoir in question. For a pilot flood to predict quantitatively the recovery to be expected in a field-wide waterflood operation, the pilot area must behave as though it were confined (surrounded by similar areas). In this study, laboratory fluid-flow models were used to determine the simplest pilot pattern, for particular conditions of mobility ratio and initial gas saturation, that would behave as though it were confined. Pilot patterns studied ranged in complexity from a single inverted five-spot to a grouping of nine regular five-spots. Only the innermost producing well in each pattern was studied. Model results showed that the optimum number of wells in the pattern depends upon the oil-water mobility ratio and the expected oil-bank size. Unfavorable mobility ratios will, in general, require more wells in the pilot pattern than will favorable mobility ratios. Pilot patterns in reservoirs which contain a dispersed, flowable, free gas saturation will require fewer wells than for the under-saturated case. The single inverted five-spot pattern was found to be unsatisfactory for predicting behavior of fully developed waterfloods. In particular, it is possible that, in reservoirs which contain a flowable, dispersed gas phase, the oil bank will never be observed at the producers due to the large amounts of free gas which continue to be produced with the oil. INTRODUCTION One method which has been used to predict the performance of a waterflood is the pilot flood. The pilot waterflood is a flood which involves only a small cluster of the reservoir wells and is located in a small, representative portion of the reservoir. The object is that oil produced from the pilot can, in some way, be related to the oil recovery to be expected from a field-wide expansion of the waterflood. However, these field pilot waterfloods have often been unreliable in the prediction of oil recovery in a fully developed waterflood. This unreliability has also been demonstrated in several laboratory studies of pilot floods. Some of the investigators have shown that there are situations in which the pilot flood oil production is far too optimistic with respect to the oil recovery in the fully de- veloped flood. Others4-G have shown that the pilot results can also be pessimistic, especially if the pilot waterflood is initiated in an oil reservoir which has been depleted by primary recovery and is at very low pressure. The major reason for this unreliability of pilot water-floods is the migration of fluids into or out of the pilot area. By the well-known method of images, if straight lines can be drawn to represent vertical planes of symmetry in a porous medium which contains pressure sources and sinks (injectors and producers), then these lines are invariant streamlines, or lines across which there is no potential gradient, and therefore no flow. In an actual reservoir, these lines of symmetry can never be established exactly because of reservoir inhomogeneities and irregular reservoir boundaries. However, if the reservoir is relatively large and contains wells in repetitive patterns, these lines of symmetry are commonly assumed to exist for the pattern units sufficiently far removed from the reservoir boundary. Lines of symmetry for the five-spot injection pattern are shown in Fig. 1. Each five-spot unit in this figure can be considered confined with respect to flow across its boundary. In pilot floods this is not the case. The lines of symmetry for the pilot patterns investigated in this study are shown in Fig. 2. It is obvious that the fluid within these pilots is not confined and is therefore able to migrate into or out of the pilot area. Intuitively, one can see that, if more wells are added to the pilot, the innermost unit tends to behave more and more like the confined pattern. However, there is a practical limit to the number of wells which should be placed in the pilot. This limit is usually determined by economic factors. It was the purpose of this study to use laboratory fluid-flow models to determine which of the previously mentioned pilot patterns will force the innermost producing well to behave as it would in a fully developed waterflood. Since fluid migration is influenced by initial saturation conditions and the mobility ratio, these factors were included in the study. The ultimate objective of this study was to develop data which would allow the operator to choose a pilot pattern and operating conditions that will yield a production history which can be applied directly as an estimate of the performance of each production well of the fully developed waterflood. BASIS FOR THE STUDY The basic problem of field pilot floods is the migration of the reservoir fluids into or out of the pilot area. This problem has been the subject of previously reported model studies on pilot floods. These studies have been concerned mainly with the development of arbitrary "correction factors" to be applied to the simple, unconfined pilot systems such as the single five-spot. The correction factors were intended to adjust the production history of the un-

By R. S. Craig, W. E. Wallace, G. S. Kamath

The destruction of long-range order in Mg-Cd, has previously been thought to occur as a second order process. In the present work a variety of X-ray diffraction techniques are employed to show that in this case and in Mg-Cd alloys containing frorn 20 to 33 1/3 at. pct Mg the process more nearly resembles an ordinary first order phase transformation. It is found that the ordered alloy, which occurs as a single phase at lgw temperatures, transforms with increasing temperature into a Cd-enriched disordered (P) phase and an Mg-enriched ordered (a) phase. The interval over which these two phases coexist under apparently equilibrium conditiovs extends from 25" to 87°C content. At 33 1/3 at. pct Mg the two-phase region has disappeared. Measurement of the long range order parameter, s, for the ordered phase in MgCd, (from superlattice line intensities) shows that it disorders only very slightly before it is transformed into the p form. Kinetic experiments reveal that when the a phase is formed frorn the p phase by suitably quenching so as to suppress phase segregation, the transformation is essentially complete and the a phase has acquired its equilibrium value of S in less than 1 min. In an earlier investigation carried out in this Laboratory1 the rate of disordering of the MgCd3 superlattice was determined over an extensive range of temperature. The process was found to be first order and the rate constant, k, was established. At the lowest temperatures studied k was found to increase exponentially with temperature. At higher temperatures, however, it passed through a maximum and for the 100 deg interval below the point at which the superlattice was destroyed k was observed to decrease with increasing temperature. The various theoretical treatments1-3 of order-disorder phenomena lead to a negative temperature coefficient for k near the superlattice critical temperature but this region for MgCdB seemed unusually wide. Detailed analysis of the point indicated' that either the long-range order parameter, S, for MgCda varied with temperature in an anomalous way or the disordering in this instance is more complex than in the cases which have been treated theoretically. The original objective in the present work was simply to determine S vs temperature for MgCda to ascertain whether the disordering was in conformity with theoretical expectations.2° In an early stage of the work it was noted, however, that under equilibrium conditions ordered (a) and disordered (0) phases coexist in MgCd, over a considerable range of temperature. Since on thermo- dynamic grounds the coexisting phases must differ in composition, the investigation was enlarged to permit the compositions of the two phases in MgCd3 to be determined and to establish the extent of the two phase regions for alloys containing from 20 to 33 1/3 at. pct Cd.

Jan 1, 1963

By P. D. Frost, H. A. Robinson, J. R. Doig, M. W. Mote

The mechanism of hardening in heat-treatable zirconium alloys was foUNd to be analogous to that for titanium alloys. Zirconium containing a relatively large addition of a ß -stabilizing element such as molybdenum or columbium can be hardened by the following transformation: Lean alloys, having insufficient alloy content to retain ß at room temperature are hardened by the following transformation: Application of these findings in Zr-Mo-Sn and Zr-Nb-Sn alloys produced strengths as high as 190,000 psi with reasonable ductility. PRIOR research on zirconium alloys has been concerned with development of greater strengths and creep resistance by solid-solution hardening or by dispersion hardening. Although solution and aging heat treatments had been applied earlier to zirconium alloys, quenching frequently produced low ductility. The possibility that the ß-to-w transformation, discovered earlier in titanium alloys,' might also occur in zirconium alloys and cause low ductility was considered, and, indeed, was found as predicted2 to be the case. In the earliest experiments, the heat-treatment response of titanium, too, was disappointing. However, by avoiding the formation of the embrittling w phase, it became practical to obtain room-temperature strengths higher than 180,000 psi, with elongation values of 10 pct.3 Based on the present concept of titanium heat treatment, the principal requirement for a heat-treatable zirconium alloy is that it contains a certain minimum amount of one or more ß -stabilizing elements. Only molybdenum, columbium, and tantalum, when present in sufficient amounts, are known to stabilize ß zirconium to room temperature during rapid cooling from the ß field. Tantalum was undesirable because of its high thermal-neutron cross section. Aluminum and tin are effective a stabilizers, but aluminum has been shown to seriously decrease the corrosion resistance of simple zirconium alloys in hot water. Therefore, for the present study, tin was used as the stabilizer addition. The alloys selected for this evaluation are presented in Table 1 along with their analyses and ß-transus temperatures. The analyses indicated that intended compositions were usually realized. EXPERIMENTAL PROCEDURES All of the alloys were melted from sponge zirconium and fabricated to sheet for heat treatment

Jan 1, 1960

A SPRING meeting is to be held at Cleveland this month under the joint auspices of the Iron and Steel Committee and the Ohio Section with the cooperation of the neighboring sections in Pennsyl-vania, Illinois, and the other States of the Great Lakes region. The discussions will be focused on just one subject, that of manganese, but will cover that thor- oughly as is indicated by the following list of papers. TECHNICAL PROGRAM Some Political Aspects of the World Manganese Situa-tion. By C. K. Leith, Professor of Geology, Uni-versity of Wisconsin, Madison, Wis. Manganese Resources in Relation to Domestic Con-sumption. By J. V. W. Reynders, Consulting En-gineer, New York, N. Y. Manganese Deposits of the' Gold Coast, Africa. By Sir Arthur E. Kitson, Director of the Geological Sur-vey of the Gold Coast, London; with Notes on the Petrology of Certain Associated Manganese Silicate-bearing Rocks. By Maj. N. R. Junner. Reserves of Lake Superior Manganiferous Iron Ores. By Carl Zapffe, Manager, iron ore properties, North-ern Pacific Railway Co., Brainerd, Minn. Iron Manganese Alloys Low in Carbon. By. Sir Robert Hadfield, Hadfields, Ltd., London. Manganese in Non-ferrous Alloys. By M. G. Corson, Consulting Engineer, New York, N. Y. Importance of Manganese in the Steel Industry. By H. M. Boylston, Professor of Metallurgy, Case School of Applied Science, Cleveland, Ohio. Minnesota Manganiferous Iron Ore in Relation to the Iron and Steel Industry. By T. L. Joseph, E. P. Barnett and C. E. Wood of the North Central Min-ing, Experiment Station, U. S. Bureau of Mines, Minneapolis, Minn. Representatives of the leading steel companies, the Army, the Navy, the Geological Survey, Bureau of Mines, and leading technical societies will be present and a lively discussion of the various papers is already assured. Nearly 14 pounds of manganese is needed for every ton of steel made. Estimates indicate that the total reserves of ore in this country suitable for making ferro would hardly supply domestic requirements for ten years, even if it could all be mined in that time. The grade of ore called for by present practice must come from abroad. The present tariff policy of this country is stated to cost industry $8,000,000 in order to force production of manganese ore to the extent of $600,000. What is the wise thing to do? Should a stock be accumulated? If so, how? Is it feasible to change practice and use low-grade ore or to beneficiate the ores of this grade and meet our requirements? What progress is being made in this direction? ,These and similar questions are raised in the various papers that have been submitted and will be open for dis-cussion.

Jan 3, 1927

By Gerald Edmunds

THE liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the com- position of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. APPARATUS By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 1 ¾ in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 18 ½ in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

By William R. Webster

I have continued the investigation of the Pottstown Iron Com pany's basic Bessemer keel plates on the line referred to in my paper of last October (Trans., xxi., 766)) and have added a study of the hardening effects of sulphur, which were not taken into account at that time. The results are so encouraging that I now give them in full. For some months we have graded all the steel at these works by the table given in my former paper, and checked the grading by the forging-tests as described in the paper of Mr. Joseph Hartshorne, read at the same meeting (Trans., xxi., 748). The steel thus graded was bloomed for the plate orders. Then one slab was rolled into a plate for the order, and a tension-test was made of this plate. By the result of this tension-test we were guided in rolling the balance of the heat. Out of several hundred heats graded in this manner, 95 per cent. met the requirements of the orders in every respect, and were accepted; but these results will no doubt be improved upon, when the influence of sulphur is also considered.. The hardening effect of sulphur seems to be about 500 pounds per each .01 per cent. of increase. In the table accompanying the pres ent paper, the ultimate strength with .06.5 per cent. sulphur agrees with the old table where sulphur was not considered; that is, for all steels with less than .065 per cent. sulphur we now get lower re sults, and for those with more sulphur, higher results. Making this allowance for sulphur, the assumed ultimate strength of a 3/8-inch plate of pure iron is reduced from 38,000 pounds per square inch to 34,750 pounds. With this as a basis, I have constructed my new table, giving each of the elements, carbon, phosphorus and manganese the same hardening effect as before, to wit : Carbon is credited with a constant effect of 800 pounds per each, 0.01 per cent. Phosphorus shows greater effect in high-carbon than in low-carbon steels. For 0.07 and 0.08 C, it has about the same effect as carbon, that is, 800 pounds for each .01 P. This increases to 1500 pounds per .01 P in 0.15 C steel, or nearly twice the effect of carbon. This

Jan 1, 1894

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

By L. F. Mondolfo, B. E. Sundquist

The undercooling associated with the nucleation of the secondary phase from the liquid by the solid primary phase was studied in sixty binary alloys by means of a hot-stage microscope. It was found that in a system of a and ß, a usually nucleates ß at low undercoolings, but ß does not nucleate a, except possibly at undercoolings approaching homogeneous nucleation. This behavior can be explained in terms of relative interfacial energies and shows that crystallographic disregistry is only a minor factor in heterogeneous nucleation from metallic liquids. PREVIOUS experimental work1-6 on nucleation of solids from liquids has shown that normally nucleation is heterogeneous, and that small solid particles present in the liquid are responsible for the nucleation. These experiments and the theory that has evolved from them have made apparent that there is a "characteristic undercooling" associated with the nucleation of the solid from a given liquid by a given impurity. Little is known, however, about the chemical and structural relationships between the nucleating agent and nucleated solid that control the effectiveness of the nucleating agent in catalyzing the nucleation, as measured by the required undercooling. A review of the literature has yielded seventeen undercoolingsL-6 for the nucleation of solid from liquid metals by "known" nucleating agents. All values come from experiments in which the metal studied was divided into a number of particles (10 to 300 pin diam.) much larger than the number of extraneous impurity particles so as to obtain a large number of particles free of foreign nucleating catalysts. Known nucleating agents are then introduced by coating the droplets with particles or a thin film of the catalyst. Six of the seventeen undercooling values referred to cases where, for various reasons, the identity of the nucleating species was not at all certain. Another six cases involved nucleating agents with a crystal structure that was not known. Four other cases involved undercoolings listed as greater than or equal to undercoolings which were very likely those for homogeneous nucleation. One investigation3 involved adding to droplets powdered oxides, carbides, and so forth that were doubtlessly covered with adsorbed oxide or nitride films. The highly variable nature of these films resulted in highly variable undercooling (as was also found in preliminary work in this investigation). It is apparent that the information on heterogeneous nucleation in liquid metals is too limited to give rise to any definite conclusions on the nature of the catalytic process. With these problems in mind a new method was

Jan 1, 1962

By D. E. Hartman, J. M. Roberts

A detailed study of the temperature dependence of the critical stress, TB . necessary to cause a damping loss of 1.41 x 10-6 g mm per mm3 in pre-strained magnesium single crystals has been carried out in the temperature range 82" to 320°K. Tb is found to be linearly related to the reciprocal of the ahsol~cte temperature in this temperature range. The temperature dependence of the anelastic limit, TA, defined as the stress necessary to form open unidirectional stress-cycle damping loops has been measured between 82" to 320°K. ta is found to be independent of temperature in this range. It is suggested that TA is determined by the stress necessary to activate Frank-Read dislocation NUMEROUS studies1-9 have been reported concerning the details of yielding and microstrain near and below the generally discussed macroscopic flow stress. The work of Kramer and coworkers10-13 is helpful in determining certain qualitative facts. concerning preyield phenomena. The absence of a stress-dependent delay time in annealed copper and aluminum single crystals between 83" and 298 suggests that the preyield mechanism is temperature-independent in this range. This is not sources. The temperature and stress dependence of the effective activation volume (Veff) has been measured in the damping-loop region in prestrained magnesium single crystals. The data suggests that Veff/kT is approximately constant, equal to 2 4.5 sq mm per g in the temperature range 130°to 298°K, and that Veff is almost independent of stress at stress levels greater than 10 g per sq mm. A restricted model is developed to predict the stress (rb) necessary to cause a small fixed damping loss as a function of temperature, effective activation volume, and dislocation density. Various possible dislocation mechanisms controlling TB are discussed. true for zinc, p brass, and iron crystals in the same temperature range, however, since the existence of a stress-dependent delay time suggests a thermally activated preyield mechanism in these materials.10-13 The work by Vreeland et a1.14 confirms the work by Liu et al.ll on delayed yielding in zinc single crystals. A stress-dependent delay time between 82" and 298°K was found12 in prestrained aluminum and copper crystals. These results suggest that the preyield phenomena may be different between prestrained and unstrained or annealed crystals. The temperature dependence of the yield point at 2 x 10-8 plastic strain found by Rosenfield and Averbach3 in annealed copper and aluminum is not in agreement with the delay-time data, unless possibly the delayed yielding experiment only de-

Jan 1, 1964

By C. R. Ramachandra, C. C. Patel

Flotation of chalcopyrite from a low grade ore was studied by using different xanthates and dixanthogens as collectors and by conditioning the flotation pulp with oxidizing gaseous systems. The improvement in the recovery of chalcopyrite with the oxidizing systems was mainly due to the auto-activation of chalcopyrite, leading to the enhanced adsorption of xanthates and dixanthogens even when the latter were formed by oxidation of the xanthates. With air or oxygen as oxidizing system, the amount of ethyl xanthate required at pH 8.5 was much less than normally employed in the industry, the recovery being 97-99% of chalcopyrite with a concentrate of 24% copper. With isopropyl and isoamyl xanthates, the recovery was improved but the grade was lowered. By conditioning the pulp with air-CO2 or oxygen-CO2 mixture, the recovery was lowered with ethyl xanthate only, mainly due to the depressant action of bicarbonate formed. Flotation with dixanthogens gave cleaner concentrates of chalcopyrite. because iron pyrite did not float with these collectors. Of the dixanthogens tried, diisopropyl dixanthogen gave the highest recovery, 99% chalcopyrite with a concentrate containing 28.5 to 30% copper, when the pulp at pH 8.5 was condi-tioned with air. Isopropyl dixanthogen was found to be the best collector of all the xanthates and dixanthogens studied. It was found that the adsorbed ethyl, isopropyl and isoamyl xanthates at chalcopyrite surface, activated by cupric sulfate, and at iron pyrite surface were oxidized to the corresponding dixanthogens to different degrees in presence of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture.' The dixanthogen formed at chalcopyrite surface was, however, firmly adsorbed while that at iron pyrite surface was easily desorbed. Since dixanthogens formed have greater hydrophobicity than the corresponding xanthates, as revealed by contact angles,1,2 the former were expected to improve the flotation results. It was, therefore, thought desirable to find out the effect of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture on the selective flotation of chalcopyrite when individual xanthates were used as collectors. The effect of direct use of dixanthogens as collectors on the selective flotation of chalcopyrite was also investigated. For these studies, low grade chalcopyrite ore, received from the Indian Copper Corp., Ltd. (I.C.C.), Ghatsila, Bihar, was employed. At the milling plant of the I.C.C., chalcopyrite is floated at a pH of 8.5, employing ethyl xanthate as collector. EXPERIMENTAL Materials Employed: XANTHATES - Ethyl, isopropyl and isoamyl xanthates of potassium were prepared in a pure state by the methods described earlier.4 A 0.03% aqueous solution of a xanthate was freshly prepared in air-free distilled water for flotation studies. DIXANTHOGENS - Diethyl, diisopropyl and diisoamyl dixanthogens were prepared by the oxidation of xanthates by iodine and purified by extraction with petroleum ether. A 0.03% alcoholic solution of dixanthogen was used as a collector. FROTHER - A 0.2% solution of pine oil in ethyl alcohol was employed. SODIUM CARBONATE - A 0.4 N solution was used. ORE - The composition of the -100 +200-mesh size (Tyler standard) powdered ore, as determined by standard methods of analysis, was: copper 1.57%, iron 10.29%, sulfur 3.15% and acid insolubles 66.10%. Iron present as chalcopyrite (CuFeS2) was 1.38%, while that present as iron pyrite (FeS,) was 1.37%. Both chalcopyrite and iron pyrite were found to be liberated from the gangue minerals and from each other, as observed under a microscope. Flotation of Chalcopyrite with Xanthates in Presence of Different Gaseous Systems: Fifteen grams of -100 + 200-mesh size ore were shaken well with 100 ml of distilled water. The pH of the pulp was adjusted to 8.5 by the addition of sodium carbonate solution. Then 0.1 ml of xanthate solution (0.005 lb xanthate per ton of the ore) was mixed with the pulp, and the latter together with washings transferred to a

Jan 1, 1963

By Emmanuel P. Papadakis

Ultrasonic velocity measurements have been made to study the preferred orientation in cube-textured copper. Methods applicable to thin specimens were employed since the specimens were necessarily of sheet material. The measured velocities in various directions in the sheet differed from the corresponding values in single-crystal copper by 1 to 6 pet. The distribution of the deviations indicated that the align-ment of the (001) planes with the rolling plane was better than the alignment of the [100]and [010] directions with the rolling and transverse directions. Ultrasonic pole figures (velocity us orientation) are shown to be useful in the study of preferred orientation. THIS paper describes one set of experiments in a continuing study of preferred orientation in worked metals. This study has been undertaken to investigate the fundamental properties of metals when used as propagation media for ultrasonic waves. Many such materials are of current or potential use in ultrasonic delay lines. Fundamental studies on ultrasonic propagation parameters such as velocity, attenuation, and diffraction (beam spreading) are of importance in the design of delay lines, in the development of nondestructive testing methods, and in the study of materials themselves. Preferred orientation in worked poly-crystalline metals influences all three above-mentioned parameters, and hence is of particular importance. When polycrystalline metals are subjected to mechanical working, they develop textures dependent upon their crystal structure and the symmetry of the working operation.' The texture consists in the alignment of the crystallographic axes of the grains in preferred directions with respect to the symmetry axes of the working operation. Since the grains are elastically anisotropic, the elastic moduli of worked metals are anisotropic. Hence the velocities of elastic waves in worked metals depend on the directions of propagation and polarization. The worked metal may be thought of as taking on the elastic symmetry of a single crystal: so it possesses the same number of independent elastic moduli as the crystal class it simulates. In general, a worked metal does not adopt the crystalline symmetry of its own grains. For instance, most rolled sheet becomes effectively orthorhombic while all bar stock and wire develop hexagonal symmetry. However, certain metals with cubic crystal structure develop a cube texture upon rolling and annealing.= Nearly perfect alignment of [100]-type directions with the rolling direction, transverse direction, and rolling-plane norma1 can be achieved in certain fcc metals and alloys. These cube-textured rolled metals provide an excellent opportunity to test preferred orientation by means of elastic waves, since a worked metal with 100 pct cube texture would have elastic moduli identical to the moduli of its constituent metal. It is the purpose of this paper to present the results of an investigation upon cube-textured copper. Ultrasonic waves were used. The methods of measurement and the experimental results on the effective moduli will be given. The ultrasonic measurements will be shown to complement X-ray pole figures for the determination of preferred orientation in worked metals. EXPERIMENT To study cube - textured material, it was necessary to use thin-sheet material since a severe reduction in gage (95 to 99 pct) is necessary to produce cube texture. Special ultrasonic methods were needed to investigate the thin material at megacycle frequencies. A) Materials. The cube-textured material tested was a copper alloy containing 1 pct Zn. Specimens already measured for Young's modulus4 by Alers were kindly supplied by him. The specimens were slabs 3.00 by 0.25 in. cut from sheet 0.047 in. thick. The orientations of the long axes of the specimens with respect to the rolling direction were taken in 15-deg steps from 0 to 90 deg. B) Measurements. Two distinct experiments were performed to measure the phase velocity in these specimens. One measured the shear wave velocity for propagation in the 0.25-in. direction and polarization in the 3.00-in. direction. The other measured the velocity of both shear and longitudinal waves propagating in the thickness direction in the sheet. 1) Plate-Mode Measurements. The velocity of the zeroth-order shear mode5 was measured in the 0.25-in. direction in each strip. The specimens were ground thinner over half their length to assure that the first-order shear mode would be cut off below 6 Mc per sec, leaving the zeroth-order nondispersive shear mode as the only propagating mode. Piezoelectric ceramic transducers of 5 Mc per sec resonant frequency poled in their long direction were solder-bonded to the edges of the thin part of the slabs as in Fig. 1 after these edges had been made flat and parallel by fine grinding. These transducers produced waves polarized in the 3.00-in. direction and propa-

Jan 1, 1967

Jan 1, 1936

By M. C. Flemings, R. Mehrabian

In a recent series of papers,1-3 it was shown that a variety of apparently different types of macrosegrega-tion result from the same basic mechanism, the inter-dendritic flow of solute rich liquid to feed solidification and thermal contractions. The important parameter governing sign and extent of segregation was shown to be (v.?T)/ where v is interdendritic flow velocity, ?T is temperature gradient, and E is rate of temperature change. It was proposed in one of the previous papers that the "negative cone of segregation" often found at the base of large ingots results from the large value of (v. VT)/E expected to pertain there. The reason why this parameter is expected to be large in that location is the high flow velocity to be expected there, as discussed earlier,' and as shown schematically in Fig. 1. In this note, two experiments are summarized which are intended as laboratory simulations of the inter-dendritic flow behavior sketched in Fig. 1 and, therefore, of the "negative cone of segregation". Experimental procedures employed are as described in the the earlier work.3 Alloy cast was nominally Al-4.5 pct Cu. Fig. 2 shows one of these ingots, a "prism" ingot, 6 cm high by 12 cm wide by 10 cm long, unidirectionally solidified from a water cooled base. In this ingot, in-terdendritic flow velocity increases near the upper portion of the ingot because of the gradually decreasing ingot cross-section. Calculations were presented earlier of the negative segregation to be expected in this type of ingot,' and results presented in Figs. 2 and 3 agree closely with those of earlier calculations. A more direct (although less easily calculable) simulation of the "negative cone of segregation" is the

Jan 1, 1970

By A. B. Kinzel

SILICON, unfortunately, is not in the same category as some other metals with respect to the absolute value of the highest purity material prepared. Tucker, in England, and Becket, in this country have devel-oped procedures for the purification of silicon, and Becket's process has made industrially available silicon of a purity of 99.8 per cent or better. However, even the term "silicon metal" may be a paradox to some people, although not more so than the term "amorphous" as applied to silicon. These terms come from commerce, and "metal" is used to distinguish industrially high-purity silicon from ferrosilicon, silicon-aluminum, and other high-silicon alloys. Alloys of iron and silicon with 95 per cent Si or less are known as ferrosilicon, with a designation of silicon content where necessary, and the terns "silicon metal" is invariably applied to the grades containing 96 per cent Si and higher. The Becket method of purification was referred to in a monograph on the Alloys of Iron and Silicon, and the Tucker procedure was described in some detail in that publication.1 In order to get silicon of still higher purity, a sample, prepared by the Becket method, analyzing 99.84 per cent Si, 0.020 Fe, 0.016 Al, 0.005 Ca, 0.025 C, 0.033 per cent 02, 0.006 H2, 0.006 N2, and 0.001 per cent Mn, was crushed to pass a 100-mesh sieve said further purified by a modification of Tucker's procedure. This modification differs from Tucker's method in that after treatment the 100-mesh alloy was centrifuged to remove the last traces of acid. Our directly determined analysis of this purified sample shows: Si, 99.952 per cent; Fe, 0.009; Al, 0.012; Ca, 0.003; C, 0.006; or 99.982 per cent. Silicon by difference equals 99.97 per cent. The variation between silicon by difference and silicon as directly determined is important. Although Tucker mentions the amount of insoluble matter in commercial silicon both before and after his treat-ment, he does not mention the existence of carbon in the alloy; neverthe-less, lie reports silicon by difference. Any final figure as to purity obviously results from agreement between direct determination and

Jan 1, 1939