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By T. A. Pollard, C. R. Sandberg, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By C. R. Sandberg, T. A. Pollard, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By M. Takeda, H. Majima

Pyrite has been subjected to xanthate adsorption experiments in order to determine the nature of adsorption. The identification of adsorbed species by means of IR spectroscopy, as well as UV, shows that the dixanthogen adsorption is undoubtedly predominant on pyrite surface. The rest potential measured in a xanthate solution coincides with the redox potential of the xanthate-dixanthogen couple. Considering all the factors together, the adsorption mechanism of dixanthogen on pyrite has been proposed as This mechanism is consistent with the "passive" character of pyrite. From the measurement of the redox potential of the xanthate-dixanthogen couple in the homologous series, a rule similar to that for surface tensions proposed by Traube is also applicable. The polarization experiments were conducted on pyrite in a solution containing xanthate. In the anodic polarization, xanthate is observed to oxidize to dix- anthogen, which depresses oxygen evolution on py rite at higher potential levels. In spite of the importance of the presence of pyrite in the flotation of sulfide minerals, not many studies have been made on the xanthate-pyrite system in the absence of an activator or a depressant. In an early study by Gaudin and Wilkinson,' it was pointed out that no ferric xanthate was formed on a pyrite surface, while in another study Gaudin and his collaborators2 proved the formation of a very small amount of ferric xanthate. Afterwards, Gaudin et al.3 studied the pyrite-xanthate system with a radiometric technique and found indications of the presence of adsorbed dixanthogen on pyrite surfaces. Mamiya4 studied the flotation behavior of the pyrite-xanthate system and also suggested the possibility of dixanthogen. Recently, Fuerstenau and his coworkers at The Colorado School of Mines5 studied the role of dixanthogen in the xanthate flotation of pyrite and discussed the problem in terms of such properties as oxidation potential, zeta potential, flotation recovery, pH of solution, etc. However, the mechanism of dixanthogen adsorption at the pyrite-water interface is not yet understood. This paper is concerned with an electrochemical in-vestigation through which the mechanism of dixanthogen adsorption on pyrite is interpreted. EXPERIMENTAL MATERIALS AND TECHNIQUES Pure potassium xanthates were synthesized by an

Jan 1, 1969

Today, the employment of the modern hammer drill, using hollow steel, with air or water to expel the cuttings from the drill hole, is the rule rather than the exception in practically all rock-drilling operations. There is considerable carelessness in the matter of keeping the hole in the drill steel properly opened. Plugged steels wholly or partially, prevent proper operation of the drill, whereby drilling speed is retarded, water tubes are bent or broken, and time is lost in tink-ering, or, as often happens, the drilling gang is idle while someone makes a trip to the shop after another drill steel or water tube. To relieve this condition, the Ingersoll-Rand Company has developed, as an auxiliary to the Leyner sharpener, a new device-the Leyner shank and bit punch.

Jan 4, 1918

By Enrique Touceda

FOR a number of years prior to the world war, the firm of Geo. H. Thacher & Co., of Albany, N. Y., was engaged in the manufacture of marine and other gray-iron castings. At -the outbreak of the war the firm decided to specialize in the manufacture f propeller wheels. It attacked the problem, therefore, from a foundry point of view, seeking to produce a casting that would be so accurate that no subsequent machining would be required on the blades, also from the point of view of the ship builder. There were two general methods f manufacture, the shortcomings of which have been freely acknowledged. In the sweep method, the nowel, or bottom half-mold, for each blade is swept up by a spindle beam and pitch race, while the top half-mold for each blade is built up individually. In the pattern method one individual blade, with the hub or hub portion, is mounted on a spindle and the individual -blade mold formed, the pattern is then rotated on the spindle to the position- for the next blade, etc. In rare cases wheels were made from a solid pattern. Owing to the cost of the pattern, its failure in many instances to be correctly made, and (when made of wood) its early and sure distortion the disadvantage of this practice is obvious, while metal patterns in most instances were prohibitive in cost. In these methods both green-sand and loam molding was practiced. The casting produced by either method can be considered only as a blank from which the propeller must be machined. The back surface f each blade must be chipped too the templet and through this procedure chipped to such accuracy, as will be required for a static balance. Inasmuch as the' work done by the machine tool is confined to the driving face of the blades, not only is perfection most difficult, but corrosion will be greater because of the removal of the dense skin f the casting and the local strains set up by the pneumatic tool in chipping. To produce a finished 9-ft. propeller for a Navy destroyer required from 8 to 21 days f foundry work and about the same length of, time for the machining. Through the use f the Thacher process, only as many hours are required, besides it is possible to produce a finished casting in perfect conformity, with any particular propeller-wheel design,

Jan 4, 1921

By James Boyd

Scientists and engineers must concern themselves not only with technical problems, but with the socio-economic difficulties of our scciety. The author states that raw materials are basic to the economic process and that mineral raw materials occur naturally in nearly limitless quantities. He feels that the economic pocess will provide sufficient raw materials for man's needs, and discusses in some detail the world economic environment. As our society grows in complexity, it becomes more urgently incumbent upon scientists and engineers to bring their experiences to bear on the solution, not only of technical problems, but also on socio-economic difficulties. It is to this field that I have directed a large part of my energies. RAW MATERIALS BASIC TO THE ECONOMIC PROCESS There are certain premises, frequently overlooked, which bear emphasis. As economics concerns the production, distribution, and consumption of goods, so our whole society is based on raw materials. Without the basic extractive industries of agriculture and mining, there would be no economic problems with which to deal. This principle has been expressed as "All productivity is based on three factors: 1) natural resources, whose form, place, and condition are changed by the expenditure of 2) human energy (both muscular and mental), with the aid of 3) tools.77* It seems strange that such an obvious statement needs to be made. It is forgotten by all of us, however, at one time or another when we get involved in the complicated theories of economics dealing with the financial and fiscal policies of the various governments, in the financing of enterprises, in marketing, and in labor relations. Unless decisions in all of these fields are made with this, and the rest of the "Ten Pillars of Economic Wisdom," consciously in mind, the resultant policies are doomed to eventual failure, whether these are policies of individuals, companies, or governments. The economic process is basic to society. But economics and the social aspects of humanity are inevitably intertwined. If human needs are not provided for within the basic economic structure, conflicts arise to disrupt the most carefully laid social plans. Similarly, it is the failure of society to cope with basic economic prerequisites that leads to discord within the body politic and thus to eventual economic disaster. We who are engaged in the various aspects of the mineral industry, therefore, have a large part to play in society's future development. MINERAL RAW MATERIALS OCCUR NATURALLY IN NEARLY LIMITLESS QUANTITIES Throughout my career in and out of government, I have formed my decisions on two principles: 1) Fundamentally, all mineral raw materials exist within the earth's crust in quantities greatly exceeding man's needs; 2) Any problems of supply of these materials are primarily economic in nature. With respect to my first assumption, analyses by geochemists enable them to estimate the quantities in which each of the known elements exist in the earth's crust. One of the most cautious and famous suggests that the average copper content of the lithosphere to a depth of ten miles is about 55 ppm. If this is valid, then the lithosphere contains about 1.4 quadrillion (1.4 x 10 ") tons of copper metal — an unimaginable quantity. This is 8,500,000-fold that which has been consumed by man in his existence. To illustrate further, consider that the deepest copper mine in history went to about 9000 ft below the surface; the present copper mines of the world now average less than 1500 ft in depth. We can assume that in most continental land areas of the world it is technically feasible to mine to a depth of at least one mile. The land areas of the world to an average depth of one mile, then, contain 343 billion tons (343 x 10') of copper metal, or 2000 times that which has been extracted to date. I don't believe man will ever expend his energies to extract copper from rocks which contain only a few parts per million, but he knows that each element

Jan 1, 1968

By W. C. T. Yeh, T. G. Oakwood, A. A. Hendrickson, R. H. Hammar

The objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for by the influence of the solute addition on the dislocation structure oj- the crystals. The additions of both tin and indium produced only small changes in the dislocation densities and arrangements in silver crystals. However, as found previously, small solute additions have large effects on the tensile properties; the inj-luence of the tin and indium additions on the temperature dependence of the flow stress and the easy-glide range is especially strong; It is concluded that the indirect strengthening effect of the solute due to variations in the dislocation density as proposed by Seeger is of minor importance and that solute atom-dislocation interactions are responsible for the observed strengthenirzg effects. The experimental results were combined with those of Rogausch to test the concenlvatiorz dependence of solute strengthening. Both the first and one-half power dependences of the critical resoleed shear stress on concentratiorz fail in very dilute solutions. THE objective of the research is to determine whether solid-solution strengthening effects observed in dilute solutions of silver can be accounted for, at least in part, by the influence of the solute addition on the dislocation structure of the crystals. It is recognized that the addition of solute atoms may influence the strength properties of a metal through both "direct" and "indirect" effects. The former refer to the strengthening mechanisms that result from the interaction of solute atoms with dislocations; in the latter case, the strengthening effects arise as a result of solute's influence on quantities such as dislocation density, dislocation arrangement, stacking-fault energy, diffusivities, the elastic constants, and so forth. It is clear that the correct interpretation of solid-solution strengthening phenomena cannot be given until the importance of indirect strengthening effects is properly evaluated. In the particular case of close-packed metal crystals, Seeger showed that solute strengthening effects in dilute solutions of copper and silver might be accounted for by an increase in dislocation density due to the addition of the solute. Seeger's argument was that the strengthening effects extrapolated from more concentrated solutions indicate that small concentrations of impurities raise the critical resolved shear stress much more than is predicted by a concentration-independent dislocation density. The above idea was a very reasonable one. The dislocation theories of work hardening of Taylor,2 Cot-trell, 3 Mott, 4 and seeger5 had already associated the increased flow stresses with increased dislocation densities in deformed metals; investigations of the dislocation structure of metal crystals had provided a logical basis for expecting an increased dislocation density in crystals containing impurities (see for example, Ref. 6). The numbers involved seem reasonable, too. It can be expected that the flow stress of the crystal would increase as the one-half power of the dislocation density.' Solute additions of 1 at. pct to metal crystals result in strength increases by factors in the range of three to ten. If one assumes that the strengths of the pure metal crystals are determined by their dislocation densities, then dislocation-density increases of one to two orders of magnitude as a result of solute addition would be required to account for the observed strengthening—not an unreasonable expectation. In addition to the effect of the solute addition on dislocation density, one might also anticipate important strengthening contributions to result from the solute's influence on the dislocation arrangement. Parker and washburns have reviewed a number of experimental evidences which show important strengthening effects due to the presence of subboundaries. Further, lattice strains due to impurity segregation would be expected to influence the distribution as well as the dislocation density of the as-grown crystal. As pointed out in the reviews of Chalmers,6 Elbaum,9 and winegard,lo micro segregation of impurities occurs at all interfaces of crystals in cellular growth; the impurity gradient results in lattice strains which can be reduced with the presence of dislocation arrays in the region of the impurity gradient. Hence, one would expect the presence of a solute to favor the formation of dislocation subgrain structures and that the subgrains would have an important influence on the strength of the crystal. The experimental observations that concern the possibility of an important strengthening contribution through the influence of the solute on the dislocation density or arrangement are not in agreement. Haasen has reviewed the observations of Meakin and Wils-dorf,12 Howie,13 and Bocek 36 and concluded that the solute's influence on dislocation density is not sufficient to account for strengthening effects in concentrated solutions but might, as seegerl suggested, make an important contribution in very dilute solutions. On the other hand, Hendrickson and Fine 14 concluded that changes in the dislocation density and dislocation width accounted for the solid-solution strengthening effects observed in silver-based aluminum solid solutions. Goss et a 1.I5 observed dislocation arrays in Ge-6 at. pct Si, Ge-0.2 at. pct Sn, and Ge-0.2 at. pct B crystals that were not observed in germanium crystals of

Jan 1, 1968

By David W. James, Howard Jones, George M. Leak

Conditions are described for producing, by primary recrystallization, a matrix suitable for the growth of large grains near (110)[001] orientation in silicon iron strip by secondary recrystallizaliun in a steep temperature gradient. The orientation distribution of these large grains is expressed in terms of rotational deviations about the cross-rolling direction, the rolling direction, and the normal to the sheet, the deviational spread increasing in that order. With the aid of cowplenientary published data on the orientation dependence of growth rate, it is shown that this observation is consistent with the oriented-growth theory of recrystallization lextures. It is conclutled that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally Produced recrystallization textures. SEVERAL authors have reported methods of growing large grains by re crystallization of a small-grained matrix in silicon iron 1- B and pure a cr The present study was a preliminary in the growth of single crystals and bicrystals for surface relaxation," grain boundary mobility, and grain boundary diffusion studies. The method was to control the growth of a seed crystal into a suitable primary re crystallized matrix by feeding through a steep temperature gradient. The driving energy for growth derived from the grain boundary energy released as the seed crystals grew into the matrix. Thus, stability of the matrix against normal grain growth was considered to be essential for success. It was known that the manganese sulfide dispersion present in commercial silicon iron performs this function during secondary recrystallization to the (110)[001.] texture.12 Hence commercial, rather than high-purity, material was used throughout. The paper describes the growth conditions for grains large enough to be used as seed crystals for further growth into single crystals. The orientation distribution of the seed crystals is analyzed and its significance for the theory of recrystallization textures is discussed. EXPERIMENTAL PROCEDURE Strip material was supplied by the Steel Co. of Wales, Ltd. The chemical analysis in weight percent was Si, 2.90; C, 0.015; Mn, 0.059; P, 0.011; S, 0.027; Ni, 0.032; 0, 0.009; Fe, balance. A gradient furnace of similar design to one described previously4 was loaned from B.I.S.R.A. It consisted essentially of a vertical water-cooled copper slot projecting downwards into the hot zone of a molybdenum furnace. Hydrogen was passed through the furnace to protect both heating element and specimen from oxidation. Strip specimens up to 8 cm wide and 0.2 cm thick were sealed into the furnace at the mouth of the copper slot. A coating of light oil on the strip surface maintained the seal during translation of a specimen. The maximum temperature gradient in the region just below the copper slot was 500°C per cm over 1 cm, with the hottest point controlled at 1175°C. Several large grains would usually grow by secondary recrystallization from the primary matrix when a specimen was immersed in the hot zone for about 30 min. A back-reflection X-ray camera was constructed to facilitate rapid and accurate orientation determinations of the large grains produced. It was possible to reproduce a standard geometry, with regard to strip and camera, without the tedium of careful alignment on each occasion. Specimens, typically 4 cm wide and 75 cm long, were cut with the longitudinal axis parallel to the rolling direction of the original strip. The surfaces were cleaned by immersion alternately in a hot aqueous solution containing 2 pct hydrofluoric acid plus 10 pct sulfuric acid and in cold 10 pct nitric acid. The nitric acid etch was just sufficient to reveal the grain structure. Rolling and annealing treatments to prepare the matrix (discussed below) were followed by growth of seed crystals in the gradient furnace. The matrix was transformed to a single crystal by growth of a selected seed crystal connected to the matrix by a thin neck. 4,5 Growth was promoted by controlled feeding into the gradient furnace. Several single crystals of controlled orientation were grown successfully from seed crystals by twisting the interconnecting neck in a reorien-tation jig.4 EXPERIMENTAL RESULTS AND DISCUSSION Growth Conditions. A suitable matrix for growth of large grains was prepared starting from primary re-crystallized strip 1.9 mm thick. This was cold-rolled in two stages each being followed by a recrystallization anneal at 800°C for a few minutes. Such treatment gave the required growth matrix only if the two cold-reduction stages were each performed in several passes and in the following ranges: the first, 30 to 70 pct; the second, 10 to 50 pct. Immersion in the temperature gradient otherwise resulted in an equiaxed

Jan 1, 1967

By Lawrence H. Van Vlack, Alfred S. Keh

The distribution of sulfur in iron was found to be dependent upon the time and temperature of the treatment as well as the chemical composition of the sulfide. With higher temperatures, the sulfide phase spreads more extensively between the iron grains. A complete network, however, does not form until approximately 1300°C (2372°F), ot which temperature the dihedral angle approaches zero. Silicon has little effect on this change. Aluminum, oxygen, and manganese all modify the temperature of sulfide network formation to a higher value. The microstructures which result and have significance in relation to hot-shortness are discussed. SULFIDE inclusions in steel were recognized by metallurgists before the turn of the century. Considerable attention has been paid to them, and numerous studies have been made on the working properties of steel as affected by them. It has been suggested that ho t-shortness of steel is due to the presence of an enveloping liquid sulfide film at the grain boundaries of the steel in the range of the hot-working temperatures. However, several facts have been observed in commercial steels which do not seem to be completely consistent with this explanation: 1) the frequent absence of continuous films of sulfide as observed under the microscope, 2) the absence of hot-shortness in some high sulfur and resulfurized steels, and 3) the limitation of hot-shortness to a definite temperature range. The role that manganese plays in steel to eliminate hot-shortness is well known, but the theory behind it is still under question. Moreover, the effect of de-oxidizers such as aluminum and silicon, and the effect of oxygen are still not clearly known. In this study, the effect of heat treatments and of additions of manganese, aluminum, silicon, and oxygen upon the distribution of sulfide inclusions in iron was investigated. Both the as-cast and the heat treated structures were studied, using microscopic and autoradiographic techniques. Part of the results were interpreted in terms of Smith's' concept of microstructure. Review of Literature Metallurgists used to consider sulfide inclusions as suspended particles. It was Wohrman' who first pointed out that sulfide inclusions are soluble in liquid iron. Many observed facts may be understood on the basis of this concept of solubility. Wohrman found that small castings contain small inclusions. and larger castings contain larger ones. Also, inclusion sizes are smaller near the chilled surface. For the same size ingot, the average inclusion size in a given heat of steel depends upon the rate of solidification. That is, with slow solidification, enough time for precipitation and agglomeration of these

Jan 1, 1957

By A. H. Daane, W. J. Wunderlin, B. J. Beaudry

The solid solubility of holmium in copper, silver, and gold, determined using metallographic techniques, was found to be a maximum of 0.06, 2.4, and 3.2 wt pct, respectively, nt the eutectic temperatures. The temperatures of these eutectic horizontals, determined by differential thermal analysis, were found to be 868", 787", and 778"C, respectively. The first compound on the silver-rich side of the Ag-Ho system was found to be A&Ho2. In a study by Gold et al.,' on the effect of small amounts of soluble impurities on the electrical resistance and thermoelectrical properties of copper, traces of iron were shown to have drastic effects on the thermoelectric power due to the magnetic scattering of the conduction electrons. Since little is known about the state of the iron ion when dissolved in copper, Gold had hoped to repeat these experiments using certain rare earths as the magnetic scattering centers; because of the tightly bound 4f electrons it is not expected that their spectroscopic state would be affected by alloying. In such an experiment the sole role of the trace rare-earth impurity would be to magnetically scatter the copper conduction electrons without producing appreciable distortions in the otherwise pure copper matrix. Since holmium was chosen for such a study because of its high magnetic moment, it was necessary to establish precisely its solid solubility in copper. The study was extended to include the solvents silver and gold, so that an evaluation of the data using classical solubility parameters could be made. No previously reported work on the systems of holmium with copper, silver, or gold was found in the literature. Information on the solubility of other rare earths in these three metals is also very meager. The solubility limit of yttrium in copper was reported as less than 1 wt pct2 and the solubility of praseodymium in gold as 0.35 wt pct,3 while no references were found on solubility studies of rare earths in silver. EXPERIMENTAL Materials. The materials used in this investigation were distilled holmium prepared in this Laboratory, OFHC* copper, electrorefined silver (99.9 *OFHC = oxygen-free high conductivity. pct), and gold with the analyses given in Table I. Sample Preparation. Samples weighing 1 to 2 g were prepared by arc-melting the components together on a water-cooled copper plate under purified argon atmosphere. The samples, turned and remelted at least five times to ensure homogeneity, showed weight changes of less than 0.1 wt pct after melting. Samples containing less than 0.7 wt pct Ho were prepared by diluting 1 to 2 wt pct Ho alloys with the pure solvent, while samples with concentrations greater than 0.7 wt pct Ho were prepared directly from the metals. The samples were wrapped in tantalum foil, sealed in outgassed Vycor tubing under helium, annealed at the desired temperature for at least 24 hr, and then quenched by shattering the Vycor tube in cold water. Metallographic Methods. Standard mechanical polishing methods were used in preparing the silver and gold alloys for examination, while the copper alloys were electropolished using a 40 pct solution

Jan 1, 1963

By R. R. McNaughton

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

Jan 1, 1937

By C. E. Arnold

In attacking the problems of mining and treating large disseminated copper orebodies such as those occurring in the Miami or the Ray district of Arizona, one of the vital questions to be decided is, "What is the value of the orebody per ton in place?" The importance of this question lies in the fact that its answer helps to reach a decision concerning the method of mining to be employed. Let it be assumed for the moment that milling and smelting practice, especially the latter, is more or less standardized, and has a cost incapable of much variation, while the cost of mining has a considerable range owing to the large number of mining methods by which a mine may be exploited. For instance, a method may be adopted whereby all the available ore can be extracted perfectly clean (i.e., unmixed with barren material) at a relatively high cost; or a method may be used involving the necessary dilution of a portion of the ore with waste, in order to recover that portion, thus giving a relatively poorer extraction but nevertheless a lower working cost than the former method. Naturally, between these two extremes there lie intermediate methods. In order to arrive at a solution of a mining method problem that is of any value, it is necessary that accurate and complete estimates of mining, milling, and smelting performances and costs shall be established. By way of illustration is given a case of mining, by the system of undercutting and caving, a large orebody with an average content of 1.50 per cent. copper supposedly all in sulphide form, to which case has been applied those results in mining operations which one may fairly assume are to be expected when viewed in the light of G. R. Lehman's ore-drawing experiments, which form the subject of a paper to be presented at this meeting. It is assumed that the total costs will be as shown in the table on page 204. To attain these costs, a daily production and treatment of 14,400 tons has been assumed. Other assumptions are as follows: 15 per cent. of orebody is to be extracted clean by development work and undercutting; 63.8 per cent. (75 per cent. of 85 per cent.) is to be extracted clean by caving, leaving 21.2 per cent. part of which is to be extracted by diluting with waste, and the remainder lost. Dilution and extraction are to

Jan 1, 1917

By John P. Cosgro

THE increasing use of internal furnace-boilers for mining power-plants (doubtless due to the facility with which they may be installed by reason of their portability; the fact that they require no masonry setting, cast-iron fronts, buck-stays, etc., and practically no foundation; and the successful maintenance of their claim to equal and even superior economy, as compared with boilers of other types) warrants this description of a method of remedying an injury which may occur, to such a furnace, even though it satisfies the requirements of the formula adopted by the U. S. Board of Supervising Inspectors of Steam Vessels.2 I refer to the sagging and deformation which may result from overloading the boilers for a considerable period-say, several days. This is sometimes unavoidable under the exacting conditions of continuous day-and-night service, and (in spite of all rules and precautions, the occasional careless or unskillful work of attendants. Such a trouble is by no means unknown on shipboard, where this type of boiler is so largely employed. In the case here described, two Morrison suspension-furnaces, of half-inch steel, 14 ft. long and 45 in. in mean diameter, with ? dry-back ? boilers, were necessarily operated somewhat beyond their rated -normal capacity for several months, while a third similar unit was -in process of installation, and during this period, though the boilers were kept perfectly clean, heat seems 'to have been generated slightly faster than it was absorbed by, the water in the boilers. The corrugations of this.

Mar 1, 1905

By J. S. Bryner

In the study of metallographic specimens in the electron microscope, there is need for a method of locating the same field in both the light microscope and the electron microscope. This need arises chiefly from the fact that in the electron microscope the magnification and degree of resolution are so much higher, and the field so much smaller than in the light rnicroscope that it is often difficult, if not impossible, to identify positively what is being observed. The difficulty is increased by the fact that, because a transparent film replica of the metal surface must be used in the electron microscope, micro-constituents can be identified not by their color but only by their texture and contours. For these reasons it is desirable to obtain a series of photographs showing the same field in both microscopes in order that the appearance of common microstructures and micro-constituents in the electron microscope may be identified and catalogued for future reference. The need for a method of locating the same field in both microscopes arises also when it becomes desirable to enlarge in the electron microscope for more detailed study a particular interesting structure observed in the light microscope. Using the standard polystyrene-silicalJ replica technique, in which the silica film replica is fished from the ethyl bromide on a 1/8 in. diam zoo-mesh specimen screen, the possibilities of locating a particular area on the film in the electron microscope are rather remote. The desired structure may be obscured by the wires of the specimen screen or unrecognizable at the high magnification. A solution to the problem would be provided if a specially designed specimen screen, containing an opening which could be absolutely identified and quickly located in the electron microscope, could be fastened to the silica film replica in such a position that the desired field on the specimen would be located at the identifiable opening in the specimen screen. The design for such a specimen screen, a method for producing it, and a technique for fastening it to the silica film replica are described below. Description OF Method The Specimen Screen A simple design for a specimen screen containing an opening easy to identify and locate in the electron microscope is one with two lines of openings at right angles in the form of a cross. Such a screen is shown in Fig I. The opening at the center of the cross is identified easily and can be located quickly in the light microscope and in the objective image of the electron microscope. The specially designed specimen screens for this work were produced in quantity by electroforming. On both sides of a polished strip of copper I X 3 X 1/8 in., twenty patterns of the cross of openings were punched with a diamond point micro-hardness tester, using a load of magnitude

Jan 1, 1949

By John Henry Harden

It appears that in the earlier days of anthracite coal mining, 1824-25, the Lehigh region mined 76 per cent. of all the coal sent to market. During the same period Wyoming sent 12 and 5 per cent. respectively, whilst the Schuylkill sent 11 and 18 per cent., the number of tons marketed being in those days very small indeed. In the year 1828 the Schuylkill region mined over one-half of all the coal sent to market, and continued to do so for thirty years (with the exception of the year 1831), until 1858 ; since that date the production has declined very steadily in comparison with the other regions, until, in 1876, it was only 34 per cent. Wyoming, in the year 1820, was mining 40 per cent., but the production of all the regions was very small; in six years it declined to 5 per cent., increased to 34 per cent. in 1831, declined to 10 per cent. in 1838. Since which time the increase has been gradual, until 1873-75 Wyoming produced over 50 per cent. of all the anthracite coal sent to market. In 1867 the production exceeded that of Schuylkill, and has continued to do so since that time. In the year 1876, during the existence of the "coal combination," Wyoming lost 9 per cent.; during the same time Lehigh gained 7 and Schuylkill 2 per cent. over their relative production of the preceding year, the decrease of Wyoming being two and a half million tons, the increase of the Lehigh one million, the decrease of the Schuylkill nearly three-quarters of a million. The extraordinary production of the Lehigh region at a time of decreased demand and in opposition to an agreement with the other regions to limit the supply to the supposed demand mas the cause of the disagreement which ultimately broke up the combination of the great coal-producing and carrying companies. The Lehigh region produced very steadily, from 1829 to 1854, an average of about 22 per cent. of the whole production. From 1854

By M. J. Coolbaugh

Standard Metals Corp.'s mining and milling operation at Silverton, Colo., has found that it can justify the use of a large computer system entirely on the basis of cost savings, and at the same time receive the benefits of speed, greater accuracy, and valuable data otherwise unobtainable at a reasonable cost. The Silverton operation consists of the historic Sunnyside mine and Mayflower mill, about 300 miles southwest of Denver, which produce about 700 tpd of a complex lead-zinc ore. This operation has not yet tried to use its computer for large, involved programs such as optimizing the efficiency of an operation, linear programming, or determining economic ore limits, although these are certainly within the capability of the equipment. However, there have been enough money-saving applications in the everyday routine to justify the use of this computer system, even before branching out into the more unusual or complex problems.

Jan 8, 1968

By Henry A. Wriedt, John Chipman

Equilibrium in the reaction of hydrogen gas with oxygen in liquid nickel, iron, and their alloys has been studied at temperatures of 1500° to 1700°C. The equilibrium con^stant, 0/p, [% O], is greater in nickel then in iron by a factor of 45 at 1594 C. In the alloy steel range, the activity coefficient of oxygen is slightly increased by the presence of nickel. NICKEL is more resistant to oxidation than is iron, in both the solid and the liquid state. The solubility of oxygen,' however, is greater in nickel than in iron. The two metals and their liquid alloys constitute an interesting series of solvents in which the chemical behavior of oxygen can be studied by methods similar to those used for liquid iron.' Experimental Method The furnace assembly, including the tube for preheating the entrant gas, was the same as that described by Gokcen and Chipman. " controlled mixture of water vapor, hydrogen, and argon preheated to approximately the melt temperature impinged upon the surface of the liquid metal. The charge, weighing about 35 g, was held in an alumina crucible at constant temperature in the gas stream for a prolonged period, then quenched in a stream of cold helium, sampled, and analyzed for oxygen by the vacuum fusion method. The temperature of the liquid metal was measured by a Leeds and Northrup optical pyrometer which had been checked against a similar instrument certified by the National Bureau of Standards. The freezing point of electrolytic iron in hydrogen, taken as 153j°C, was used for frequent checks. This point and the emissivity determined by Dastur and Gokcen" established the transmissivity of the optical system. The emissivities of Fe-Ni alloys at 1535" are known from the experiments of Smith and Chipman,h nd it was assumed that the variation with temperature is parallel with that of iron. Recorded temperatures are probably accurate within k5"C. Preparation of Gas Mixtures—Since the ratio H,O:H, had to be much higher for nickel than for iron, it was found convenient to construct two separate systems for gas preparation. In both cases, the ratio of argon to the sum of the other two gases was at least 4, the proportion of hydrogen and water vapor being varied to produce H,O:H, ratios from 0.2 to 70. The primary purpose of the argon was to diminish the errors caused by thermal separation' in the gas phase. In addition, its presence lowered the saturation temperature required for a given H,O:H, ratio and minimized the difficulty of preventing condensation. Both systems were modifications of the one used by Dastur and Chipman.' For H,O:HI ratios greater than 2, welding-grade argon purified by passage over magnesium chips at 620°C was mixed with hydrogen produced in the electrolytic cell shown in Fig. 1. The design was based on a cell used by Bodenstein and Pohl," the important features of which area nickel wire cathode and sodium hydroxide solution as the electrolyte. The rate of hydrogen evolution was controlled by a calibrated ammeter and a rheostat in the circuit, the current efficiency being taken as 100 pct. Precise control of the argon flow rate at about 300 ml per min was achieved by means of a capillary flowmeter having a controlled pressure drop. The molar flow rate was measured volumetrically before each run, and a constant flowmeter setting was maintained thereafter. The A-H, mixture passed through a water saturator of the type previously described," the saturation temperature being maintained automatically with a fluctuation of k0.04"C. The tube between saturator and furnace was heated by a resistance winding. The system was of all Pyrex construction with the exception of the stainless steel tube containing magnesium chips. This was connected with the glass tubing at the upstream end by

Jan 1, 1957

PUBLIC hearings began before the Committee for Reciprocity Information on May 24, 1950, for the purpose of unearthing data and opinion that will be helpful in the forthcoming reciprocal tariff and other trade-barrier negotiations at Torquay, England, on September 28th of this year. The conference this fall will constitute the "third round" of tariff negotiations under the General Agreement on Tariffs and Trade concluded at Geneva in 1947. The United States plans to negotiate with 17 other countries on possible tariff modifications on various articles all the way from baby carriages and bottle caps to lead and zinc-bearing ores. On May 31, June 1 and June 2, spokesmen appeared before the Committee for Reciprocity Information on behalf of the domestic lead and zinc mining industries. Producers of these metals protested the inclusion of paragraphs 391 (lead-bearing ores, dust and mattes), 392 (lead bullion, lead in pigs and bars, and scrap lead), 393 (zinc-bearing ores of all kinds), and 394 (zinc in blocks, pigs or slabs, and zinc dust) of the Tariff Act of 1930, as amended in the list of articles to be considered for possible tariff concessions at Torquay. It was pointed out that although operating costs have more than doubled since 1939 tariffs on these metals were actually higher in that year than at present. This, coupled with the detrimental effects of the recent series of devaluations, has sounded the death knell for a substantial number of domestic lead and zinc mines-a most undesirable development in the face of the ominous international situation, according to these spokesmen. It was urged that higher rather than lower tariff rates are needed on these metals. The opinion was expressed that it was inconsistent to foster a high living standard in our western areas and then, once it is attained, to undermine that condition by minimizing the protection that was partly responsible for it. The main theme of some arguments implied that although every effort should be made to close the "dollar gap" abroad, serious consideration must be given the methods employed lest our national security position be jeopardized in the process. The House Committee on Foreign Affairs completed hearings on H. J. Res. 236, to provide for United States membership and participation in the International Trade Organization. Hearings began on April 19th and ran for over five weeks. Many witnesses from industry and government presented voluminous testimony, which will not be available for public distribution for several weeks. However, it is no secret that the most controversial provisions of the Draft Charter of the ITO are: (1) Article 17 (Chapter IV on Commercial Policy) which would obligate members to negotiate for the reduction of tariffs and the elimination of trade preferences; (2) Article 20 which would prohibit the use of quantitative restrictions for protective purposes; (3) Article 16 which promulgates rules to implement the principle of non-discrimination in international trade; and (4) provisions permitting the use of protective measures for promoting economic development, particularly in backward areas, even though such provisions are inconsistent with those of the three articles cited above. United States membership in the International Trade Organization is essential to the successful operation of that body in view of this country's position as the economic giant in the present international trade pattern. Many countries are reluctant to take any action toward the ratification of the charter until it is known what course America will pursue. However desirable or undesirable the ideal of free multilateral trade may be it is unlikely that this Government's participation in the ITO will materialize soon. Advices in Washington indicate that H. J. Res. 236 will not be enacted during the present session of Congress. The legislative pattern designed to secure Congressional approval of the ITO is similar to that of the St. Lawrence Seaway project. The Seaway project was pending in treaty form for several years before the Foreign Relations Committee of the Senate and when the Administration decided to incorporate this project into bill form it was found that, while it passed the House promptly, the Senate decided to pigeonhole it because of the obvious intent to circumvent the constitutional prerogative of the Senate to advise and consent to the ratification of treaties. The ITO bill may be slated for a similar fate. It is deemed essential by western Senators and Congressmen that the present session of Congress enact some form of mining legislation before its adjournment, now set for July 31st. These legislators from prominent ore-producing states do not desire to return to their home areas in the fall emptyhanded. Aside from that, it is entirely superfluous to reiterate the necessity for maintaining a healthy domestic mining industry as a bulwark against a sharp rise in the temperature of the "cold war". Now that S. 2105 has failed a new bill is taking shape in the Senate Interior and Insular Affairs Committee. It is similar in language to H. R. 8221 (to encourage the conservation and development of the mineral resources of the United States) reported by the House Public Lands Committee on May 3, 1950, but so far has failed to receive approval of the House Committee on Rules. There are some qualified observers in high circles in Washington as well as in the mining industry who favor a tax incentive program to stimulate investment in mining enterprises, as opposed to a conservation and exploration program. The Bureau of Mines and the Treasury Department have undertaken a joint study to determine the need for modification of the tax laws as they apply to mining. The study is scheduled for completion before the end of the year, and appears to be supplementary to the investigation initiated by the National Minerals Advisory Council which culminated in the submittal of recommendations to the Secretary of the Interior in December 1949. The "cold war" is largely responsible for the increased demand for metals. Stock-pile purchases and heavy industrial demand due to military needs distort markets and disrupt normal price trends. Such activity has an unhealthy influence on metal production, luring some producers into a state of dependency on the continuation of this condition. When stock-pile objectives are met sometime in the future purchases must then come to a halt unless international "fireworks" are touched off. It can only be hoped that technological improvements and further mechanization of mines coupled with the stimulus of a rising population will offset the anticipated drop in industrial demand and cessation of stockpile purchases when the international crisis abates.

Jan 7, 1950

By Thomas M. Drown

THE method usually employed in accurate determinations of sulhur in pig-iron and steel is to treat a weighed sample of borings in a flask with muriatic acid, and to pass the gaseous products through an alkaline solution of lead or silver, which precipitates all the sulphur of the sulphuretted hydrogen in the form of sulphide of lead or silver. The sulphide thus formed is subsequently oxidized by aqua regia, bromine, or other oxidizing agent, and the sulphuric acid formed precipitated in the usual way by chloride of barium. I have substituted for the alkaline metallic solution, a solution of permanganate of potash in the strength of one gramme of permanganate to 200 cubic centimetres of water, and find that it gives results quite as accurate as those obtained by using an ammoniacal solution of silver. By the employment of the permanganate it will be readily seen that there is considerable saving of time and work. In order to test the accuracy of the method, six samples of pig-iron borings were weighed out (about six grammes each) and treated identically

Jan 1, 1874

By John Henry Harden

IT appears that in the earlier days of anthracite coal mining, 1824-25, the Lehigh region mined 76 per cent. of all the coal sent to market. During the same period Wyoming sent 12 and 5 per cent. respectively, whilst the Schuylkill sent 11 and 18 per cent., the number of tons marketed being in those days very small indeed. In the year 1828 the Schuylkill region mined over one-half of all the coal sent to market, and continued to do so for thirty years (with the exception of the year 1831), until 1858 ; since that date the pro¬duction has declined very steadily in comparison with the other regions, until, in 1876, it was only 34 per cent. Wyoming, in the year 1820, was mining 40 per cent., but the production of all the regions was very small ; in six years it declined to 5 per cent., increased to 34 per cent. in 1831, declined to 10 per cent. in 1838. Since which time the increase has been gradual, until 1873-75 Wyoming produced over 50 per cent. of all the anthracite coal sent to market. In 1867 the production exceeded that of Schuylkill, and has continued to do so since that time. In the year 1876, during the existence of the " coal combination," Wyoming lost 9 per cent. ; during the same time Lehigh gained 7 and Schuylkill 2 per cent. over their relative production of the preceding year, the decrease of Wyoming being two and a half million tons, the increase of the Lehigh one million, the decrease of the Schuylkill nearly three-quarters of a million. The extraordinary production of the Lehigh region at a time of decreased demand and in opposition to an agreement with the other regions to limit the supply to the supposed demand was the cause of the disagreement which ultimately broke up the combination of the great coal-producing and carrying companies. The Lehigh region produced very steadily, from 1829 to 1854, an average of about 22 per cent. of the whole production. From 1854

Jan 1, 1877