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By R. L. Wilcox, M. L. Fuller

Owing to the nature of the die-casting process, fresllly cast alloys are undoubtedly not at equilibrium from the standpoint of alloy phase relationships. After casting, therefore, they tend to undergo phase changes, with the ultimate effeet of reaching a state of equilibrium at the aging temperature, beyond which no fnrther change takes place. This phase alteration undoubtedly is one of the primary causes of the changes in dimensions and physical properties that zinc-alloy die castings undergo during aging. It is planned to report on this problem in a series of papers of which this is the first. The writers have made a study of commercial zinc die-casting alloys over a period of several years, utilizing the X-ray diffraction technic of determining the phase composition changes in the alloys. Up to the present, two principal phase changes have been observed which are capable of causing dimensional changes: (I) the segregation of secondary constituents from the zinc-base solid solution and (2) the beta aluminum-zinc decomposition. The latter is the subject of the present paper and studies on the former will be reported upon at a future time. Scope of Study In the present investigation a special technic for the study of the beta phase in zinc-alloy die castings has been developed, making possible the determination of the period of existence of the beta phase after casting. The pure beta constituent and its decomposition have been studied in detail. The effect of magnesium and copper on the velocity of the decomposition is reported. The heat of decomposition, the eutectoid temperature arid the accompanying density change have been measured. The density change lias been calculated from data on crystal structure and the result thus obtained has been compared with the actual change.

Jan 1, 1935

By R. L. Wilcox, M. L. Fuller

Owing to the nature of the die-casting process, fresllly cast alloys are undoubtedly not at equilibrium from the standpoint of alloy phase relationships. After casting, therefore, they tend to undergo phase changes, with the ultimate effeet of reaching a state of equilibrium at the aging temperature, beyond which no fnrther change takes place. This phase alteration undoubtedly is one of the primary causes of the changes in dimensions and physical properties that zinc-alloy die castings undergo during aging. It is planned to report on this problem in a series of papers of which this is the first. The writers have made a study of commercial zinc die-casting alloys over a period of several years, utilizing the X-ray diffraction technic of determining the phase composition changes in the alloys. Up to the present, two principal phase changes have been observed which are capable of causing dimensional changes: (I) the segregation of secondary constituents from the zinc-base solid solution and (2) the beta aluminum-zinc decomposition. The latter is the subject of the present paper and studies on the former will be reported upon at a future time. Scope of Study In the present investigation a special technic for the study of the beta phase in zinc-alloy die castings has been developed, making possible the determination of the period of existence of the beta phase after casting. The pure beta constituent and its decomposition have been studied in detail. The effect of magnesium and copper on the velocity of the decomposition is reported. The heat of decomposition, the eutectoid temperature arid the accompanying density change have been measured. The density change lias been calculated from data on crystal structure and the result thus obtained has been compared with the actual change.

Jan 1, 1935

By Clarence Thom

This chapter presents, in summarized form, standard procedures for making separations of minerals from their ores by the froth flotation process to produce marketable concentrates. These are typical mineral separations which are being made commercially with the reagents and conditions generally used in the mining industry. Typical separations are presented for 17 metallic and 11 nonmetallic ores. The review of each includes a brief description of the mineral and the particular problem presented, general market specifications for its concentrates, an outline of treatment method, and kinds and quantities of reagents usually employed. This chapter does not include de- tails about ore preparation (crushing, grinding, and classification), elements of ore and pulp transportation (conveying and pumping), or concentrate preparation for market (thickening, filtering, and drying). In each presentation it is assumed, if not detailed further, that the ore is ground to the economical point of liberation of the minerals to be separated. Specific information, such as ratio of concentration and recovery, that depends upon the grade of ore being treated is considered beyond the scope of this chapter. Effective flotation separations that produce marketable concentrates may produce widely varying results in terms of percent recovery and still be economically profitable operations. Details of plant practice on specific ores are presented in Chapters 16 and 17. In this chapter the chemical names of the reagents are given. The extent to which different reagents are used in flotation plants in the U. S. is presented in Chapter 4. A compilation of the various flotation reagents, their trade names, manufacturers, and use has been prepared by H. T. Spedden. ANTIMONY The principal ore mineral of antimony, stibnite (Sb2 S3), is generally found in the U. S. in ore bodies in association with other valuable minerals such as galena (Pbs), sphalerite (ZnS), chalcopyrite (CuFeS2), or tetrahedrite (3Cu2 S – Sb2 S3), The sulfo-salt minerals of antimony, such as tetrahedrite or pyrargyrite, are often associated with high silver values, so that the presence of antimony may indicate economic importance even though the actual antimony content is low. Antimony is also significant to the mineral economy because of its occurrence in some ores where lead, gold, and silver are the

Jan 1, 1962

C. H. BIERBAUM,* Buffalo, N. Y.--I agree with Dr. Merica that the eutectoid has a distinct effect upon the alloy and also that, as yet, it is difficult to say at just what point this eutectoid occurs or the conditions under which it appears; that is, the percentages of copper, tin, zinc, lead, and the other elements together with the temperature of pouring and the rate of cooling that is necessary; all seem to have a contributing effect. Some authorities, Law for instance, gives it as 9 per cent. of tin, yet under certain conditions I have found it with a lower percentage of tin to copper contents than that. The hard delta and the soft alpha crystals are both necessary for a bearing alloy; the one supplements the other. I am not inclined to think that phosphorus has any effect upon the eutectoid forming. The phosphide, PCu3, forms in and around the delta but is and remains distinct and separated from it. Etching with ferric chloride and then with nitric acid shows this very distinctly; it darkens the eutectoid and the other parts and leaves the phosphide bright. The rate of cooling determines the size of the crystals and the eutectoid together with their distribution and orientation. It is possible to chill the alloy to such an extent Where no eutectoid appears. I think it has been positively demonstrated that only an alpha and a beta appear. when this copper-tin alloy has been poured between two polished ingots

Jan 1, 1919

By Robert L. Kidd

ONE time or another placer mining attracts the attention of a large number of people, because of the possible low initial investment, low operating cost, and quick returns. Much has been said about sampling and operating placer deposits but many are still inclined to jump at a property without giving much, if any, consideration to proper sampling. This statement does not apply to experienced mining engineers but I am hoping that readers will tear out this article and pass it along where it will do the most good and thus help to preserve the reputation of legitimate mining. It would appear that some people have an ability to sink test pits in high-grade gravel that is positively uncanny. One pit showing high-grade values proves to some property owners and promoters that the entire property will do the same. This is

Jan 1, 1937

By H. P. Rassbach, E. R. Saunders

MUCH progress has been made in recent years in the theory and practice of making stainless steel. By effective utilization of oxygen for decar-burization and more suitable alloying agents, it has been possible to attain consistent production of very low-carbon stainless steel. In order to facilitate economical production of stainless steels, the Electro Metallurgical Co. has carried out an extended experimental program that has clarified some of the complex interrelations of temperature and composition under decarburizing and reducing conditions. These results'-:' have been founded in large part on small experimental heats, and in order to confirm their validity and significance under commercial conditions, a survey of stainless steel melting practice has been made with the cooperation of stainless steel producers. Conditions required for decarburization and associated oxidation of chromium, manganese, and iron have been fairly well established in relation to the beneficial effect of the highest practicable temperature. The recovery of chromium and manganese from highly oxidized slags by reduction with silicon has been indicated with somewhat less precision and this study has shown significant deviation in large commercial heats from the small experimental heats. In spite of an unsatisfactory degree of accuracy in estimating the conditions affecting reduction of metallic values, it has been possible to calculate a slag weight in reasonably good agreement with the results observed in large heats. While there still is much to be learned about both the qualitative and quantitative aspects of stainless steel melting, this survey has indicated the manner by which the efficiency of the production process may be measured. Oxidation Period In order to establish practices for the recovery of chromium and manganese from the slag the amounts of these metals oxidized should be known. Moreover, since reduction of oxidized chromium and manganese must necessarily be accompanied by similar reduction of iron, knowledge of the total quantity of metallics oxidized is essential. The relations between carbon, chromium, and temperature under oxidizing conditions were developed by Hilty in 1948.' While it had been realized previously that retention of chromium in the metal during carbon oxidation is favored by high temperatures, the Hilty relation provided quantitative information useful for evaluating melting procedures. For example, it was shown that decarburization to moderate carbon levels can be achieved while retaining substantial amounts of chromium. However, in decarburizing to the low-carbon level necessary for producing 0.03 pct maximum carbon stainless steel, very little chromium remains in the bath at the temperatures generally employed. For this reason, Hilty, Healy, and Crafts' later projected an extension of the chromium-carbon relation to the low-chromium region. Although this chromium-carbon-temperature relation defined the composition of a chromium steel bath at the end of the oxidizing period, it did not provide a direct means for estimating the total amount of metallic oxidation occurring during decarburization of a stainless steel heat. This subject was investigated by Crafts and Rassbach³ and, later, by Hilty, Healy, and Crafts" who demonstrated that metallic oxidation is a function of the chromium content of the initial furnace charge, the minimum carbon content attained, and the temperature. It was further demonstrated from data on 1-ton heats that an empirical relationship exists between the ratio of chromium plus manganese to iron in the slag (S) to the corresponding ratio of these components present in the metal bath. The following expression was derived to permit the calculation of the amount of metallics oxidized during decarburization of a given charge: W-2000 (Cr1 + Mn1)-(Cr2 + Mn2) 1 100s/s+1-(Cr3 + Mn2) where W is the pounds of chromium, manganese, and iron oxidized per ton of charge; Cr1, the percentage of chromium in the charge; Mn1, the percentage of manganese in the charge; Cr2, the percentage of chromium in the bath after oxidation; Mn2, the percentage of manganese in the bath after % Cr + % Mn oxidation; and S =%cr+ % Mn/%Fe in the slag after %Fe oxidation. In order to establish whether the slag ratios of commercial heats are consistent with those found in the experimental heats, the slag and metal analyses shown in Table I were evaluated. These data represent samples taken after the oxidation of two 1-ton and seven 15 to 25-ton heats of types 303, 304, and 304L stainless steel made in chromite, acid, and basic hearths. Fig. 1 illustrates that the results for the commercial heats correlate reasonably well with the relationship originally established for experimental 1-ton heats. It will be noted that in the range of metal composition of these heats, the slag values generally lie above the line. As was suggested by

Jan 1, 1954

By J. S. Marsh

JOSEPH PRIESTLEY prepared oxygen on Aug. 1, 1774, and noted with great surprise "that a candle burned in this air with a remarkable brilliant flame." On Aug. 2, 1774, some ironmaker possibly began to wonder if this substance could be used to increase his rate of production; at any rate, there is no disputing the fact that the notion of using oxygen for steelmaking in concentrations greater than that available in great abundance-as air-has been in existence for years. Action was delayed by the lack of enough oxygen at a cost within reach of the steelmaker. Within the last several years enough has been available to permit large-scale tests of its use for both combustion, with which this paper is concerned, and for decarburization. The literature is now enormous and easily available; it is sufficient here to cite three items of historic- importance in that all are about 25 years old and in that all are remarkably consistent as far as they go, with what is known today.1,2,3 SIGNIFICANCE OF HIGH-TEMPERATURE HEAT The principal 'function of the open-hearth furnace is to supply sufficient, high-temperature heat to melt the charge and then to increase its temperature to a range suitable for tapping, ordinarily in the neighborhood of 2900°F. That heat is required to make steel everybody; however, there seems to be some confusion now and then about the significance of high-temperature heat. Transfer of energy-and heat is energy is always from a point of higher potential to a point of lower potential and, other things being equal, the greater the potential difference, the greater is the rate of transfer of energy. In the open hearth the flame, of course, is the high-potential source. Perhaps the most satisfactory approach is through the notion of theoretical flame temperature; which is the ratio of heat input to the heat content of the combustion products,* the former is composed mainly of heat of combustion of the fuel plus sensible heat of the fuel plus sensible heat of the combustion air. Thus, flame temperature can be increased by increasing the value of the numerator, by decreasing the value of the denominator, or both. The first method is as old as the open-hearth process and, of course, makes use of preheated air; its possibilities have been by no means exhausted. The second method can be put into effect only by changing the composition of the combustion air, since the combustion of a given quantity of fuel produces a definite quantity of product, and since the denominator includes the non-reactive fraction of the air, principally nitrogen. In other words, the denominator consists of the volume of exit gas multiplied by its heat capacity and that volume consists of carbon l is understood by dioxide and water vapor as reaction

Jan 1, 1948

By Howard Smith

AT the meeting of this Institute in February 1933, I presented a paper on potash development in southeastern New Mexico1, which contained a brief review of the Geological Survey's 20-year search for commercial sources of soluble potash minerals and of the events, that led to the discovery, exploration, and first development of the deposits in that state. As a more comprehensive review of the subject was published in December2, the present paper is intended only to discuss recent developments in the domestic potash industry, particularly in New Mexico. A summary of the findings of potash in the Permian Basin, by. G: R. Mansfield and W. B. Lang, geologists of the United States Geological Survey, is now in process of publication by the University of Texas and will be omitted from this paper. In New Mexico prospecting for potassium salts during the past two years has increased materially the known area .of commercial deposits; development has resulted in an increase from one to three in the number of shafts and the starting of a fourth; an increase of annual productive capacity to 1,000,000 tons of crude salts, or 250,000 tons of K20; and an increase in annual refining capacity to 140,000 tons of muriate of 62.5 per cent grade. Construction has been completed to increase still further the production of high-grade salts. In California the American Potash & Chemical Co., operating on Searles Lake brines, has increased its plant capacity from about 100,000 tons to 180,000 tons of muriate a year and is now producing soda ash and salt cake in addition to potash and borax. Potash production from cement-plant and industrial-alcohol wastes remains unimportant.

Jan 1, 1935

By C. L. Thornburg

FLANKING the Valley of Mexico on the northeast is a mountain range known as the Sierra de Pachuca. This northwesterly-trending range is about 30 miles long and 5 miles wide, its summit attaining an elevation of more than 10,000 feet above sea level, or 2000 feet above the valley floor. Pachuca, a town of 50,000 inhabitants, lies nestled at the southwest base of the range, 60 miles northeast of Mexico City. Three miles to the east, just over the summit and on the northeasterly slope, is the mountain town of Real del Monte with a population of about 20,000. These are the two principal towns in a 40-sq mile area whose yield has brought the district to its high rank among the world's silver producers. Total production probably exceeds 1.25 billion ounces of silver and 4.5 million ounces of gold. Exploitation by the Spanish was under way by 1530. As the mines were deepened operations became handicapped by the inadequate method of handling water with horse whims and bull skins. To offset this disadvantage a two-mile drainage tunnel was started in 1749 and completed ten years later. John Taylor of London acquired the mines from the third Count of Regla in 1824 and formed the Compania de Real del Monte y Pachuca. Two years later Cornish pumps were brought from England. A Mexican company purchased the British interest in 1848 and within a few years resumed an old project of driving a second, lower three-mile drainage tunnel, completing it in 1857. After American interests acquired control of the property in 1906 operations expanded to an unprecedented scale, despite periods of political strife, unstable prices, labor problems, and a growing burden of taxation. An idea of the scale of operations may be gained from records of the last two decades prior to 1947, the last year for which production information is at hand, during which time production ranged from 1.4 million to 1.1 million tons per year, and the combined development and exploration, exclusive of diamond drilling, amounted to about 18 miles annually. Pachuca differs from Zacatecas and some other Mexican silver vein districts that flourished and declined in earlier centuries in that a substantial part of its total production was made after 1900. While the district's accelerated activity in this century was largely due to the successful application of the cyanide process to the treatment of the ores, improved pumping methods, and new mechanical equipment, it was at the same time stimulated by the opening up of important new orebodies as a result of active and extensive exploration of the vein system. Some of these orebodies were found on veins which terminate upward far below the surface, and though these particular veins do not crop out, they show relationship with a type of alteration which may be their surface expression. The district has been studied by many able geologists, and a large store of information has been accumulated, much of which is recorded in published as well as private papers. Wall Rocks Extrusive Rocks: The Sierra de Pachuca is a thick accumulation of Tertiary eruptive rocks consisting mainly of flows, breccias, and tuffs. Numerous recognizable volcanic vents within the range itself manifest that the range was built up by material ejected from these vents. The maximum thickness of the volcanic pile is not known, but from deep exploration and from relationship with Mesozoic sediments to the north and east it is inferred that the average thickness in the main part of the district may be at least 6000 ft. The extrusive rocks comprise four general types, which in ascending order of age are: andesite, rhyolite, dacite, and basalt. The veins are confined largely to the andesite, the dominant rock of the region. Characteristically this rock is augite andesite, but it includes comparatively acidic as well as basic layers, the acidic strata being

Jan 1, 1952

By S. L. GILLAN

OF the forty or more excursions provided for the delegates to the World Engineering Congress at Tokyo, the trip to the Ashio copper mine stands out as one of the most enjoyable. In every detail looking to our comfort and pleasure the Furukawa company, our hosts, were admirable. This company operates five other copper mines, also gold and coal mines. Ashio is the largest with an annual production of about 14,000 tons of copper. It has been continuously worked since 1620, and doubtless was one of the sources of copper used in the gigantic statues of Buddha of many hundred years earlier date.

Jan 1, 1930

By H. Kazemi

An ideal theoretical model of a naturally fractured reservoir with a uniform fracture distribution, motivated by an earlier model by Warren and Root, has been developed. This model consists of a finite circular reservoir with a centrally located well and two distinct porous regions, referred to as matrix and fracture, respectively. The matrix has high storage, but low flow capacity; the fracture has low storage, but high flow capacity. The flow in the entire reservoir is unsteady state. The results of this study are compared with the results of the earlier models, and it has been concluded that major conclusions of Warren and Root are quite substantial. Furthermore, an attempt has been made to study critically other analytical methods reported in the literature. In general, it may be concluded that the analysis of a naturally fractured reservoir from pressure transient data relies considerably on the degree and the type of heterogeneity of the system; the testing procedure and test facilities are sometimes as important. Nevertheless, under favorable conditions, one should be able to calculate in-situ characteristics of the matrix-fracture system, such as pore-volume ratio, over-all capacity of the formation, total storage capacity of the porous matrix, and some measure of matrix permeability. INTRODUCTION The analysis of flow and buildup tests for obtaining in-situ characteristics of oil and gas reservoirs has received considerable attention in the past decade. Most of the available techniques result in reliable conclusions in macroscopically homogeneous reservoirs or in the homogeneous reservoirs with only certain types of induced and/or inherent heterogeneity (such as wellbore damage, etc.). In general, the greater the degree of heterogeneity, the less the reliability of the information deduced from the pressure transient data. A commonly encountered heterogeneous system is a naturally fractured reservoir where two types of distinct porosities occur in the same formation. The region containing finer pores may have high storage and low flow capacities. This is called the matrix. The remaining region may have high flow capacity with low storage. The latter region is generally the set of interconnecting fractures and fissures of the rock, and for this reason it is called the fracture. Ordinarily, we wish to obtain the permeability and porosity of each region and perhaps the frequency of the fracture distribution in a reservoir. Such information is necessary for reservoir engineering. Other information, such as wellbore damage, will be useful in evaluating possible remedial work for such fields. Few authors have suggested theories to aid in calculating the in-situ characteristics of a naturally fractured reservoir similar to what we have described above. Pollardl suggested that a naturally fractured reservoir contained three distinct regions: a damaged or an improved region surrounding the wellbore, and the two remaining regions the same as described earlier. He suggested that the flow was taking place from the tight matrix into the highly conductive fractures, then into the we wllbore region and finally into the well column. He concluded that the average pressure buildup in each of these distinct regions can be expressed approximately in terms of an exponential decay function of time. He also hypothesized that the decay coefficients for each of these functions were significantly different from each other; consequently, each of these functions became dominant in turn, in the process of pressure buildup. Thus, by a proper graphic plot of the logarithm of wellbore pressure differences vs buildup time, each of these functions could be determined (see Fig. 1). Pollard suggested methods of determining the wellbore damage and fracture volume. Later Pirson and Pirson2 extended

Jan 1, 1970

By Marcel R. Daly

EUGENE COSTS, Calgary, Alberta (communication to the Secretary*).¬This new theory to account for the accumulation of commercial deposits of oil and gas, is deliberately and admittedly based on the hypothesis that the origin of these products is organic. Mr. Daly says (page 1142), "Should the organic origin of the petroleum that is found in pools be granted, the following interpretation is offered for the mechanics of its accumulation." But suppose the origin thus accepted by definition be incorrect, then what becomes of the diastrophic theory, Mr. Daly's interpretation? As Mr. Daly remarks himself (same page), "It is obvious that the history of petroleum will have to be entirely different, dependent upon its origin, either from emanations coming from the depths, or from organic decomposition in the strata themselves." Then why should one propound a theory, through which he is endeavoring to trace the history of petroleum, by starting with a definition of its origin? The origin should be the deduction, the forced conclusion of the theory, and not its starting point. Facts alone should be considered first, in any theory worth the name, until sufficient proofs have accumulated to permit of the deduction of a complete explanation for these facts. This would lead one to the origin through a real theory founded on facts, and not based on a preconceived idea perhaps true, but possibly fanciful. Mr. Daly's way can only lead on one road, namely the organic road, and, I repeat, it may be the wrong road. In the case of the petroleum deposits, as .I have endeavored to show in several papers on the subject, to which the reader may refer, the facts clearly lead to the force conclusion that their origin is not one of accumulations of hydrocarbons at first disseminated in the sedimentary strata but the reverse process of subsequent local infiltrations and impregnations of hydrocarbon emanations from the depths. This new theory, therefore, founded on, an erroneous conception of origin cannot be a help in the solution of the petroleum' problem, not any more than were the anti-theory or the hydraulic theory, both of which were also based on the same error, although Mr. Daly is inclined to think that the authors of these two theories did not accept the misconception boldly enough (page 1142). -

Jan 12, 1916

By W. C. Lacy

Urban development in semi-arid portions of the Southwest has upset a natural balance of geological conditions resulting in broad-scale and local subsidence or heaving ground conditions, Subsidence can be traced to two general causes: irrigation of reclaimed desert lands that have dry, low-density soils; and depression of the water table by ground water withdrawal. Accumulation of weathered volcanic tuff produces areas with swelling characteristics. Soil and subsidence studies made in the Tucson area in Arizona illustrate foundation problems typical of the Southwest that must be considered in the design of building codes. Anticipation of problems and the adoption of corrective measures in the design of engineering structures, establishment of pertinent building codes, and urban planning and zoning to obtain optimum land usage and conservation of natural resources demands a thorough understanding of geological conditions of a developing urban area. In the arid to semi-arid southwestern United States erosional and depositional processes result in special situations that require special precautions in building practices. A series of studies currently underway in the Tucson area, prompted by foundation failures and breaking of buried service lines, serves to illustrate some of these relationships between the geological environment and history and engineering problems. ENVIRONMENT The desert region of the Southwest is characterized by isolated mountain ranges rising abruptly from low valleys or plains — the ranges generally occupy less area than do the intervening valleys. In southern Arizona the valley floors step up from near sea level to 2000 ft or more in elevation, and the ranges may rise to over 7000 ft. Desert and steppe-type climates predominate — climate is controlled more by elevation than it is by latitude. Both climate types are characterized by a lack of precipitation, the former more so than the latter. Practically all the rain that falls in the region evaporates; runoff or recharge generally occurs only during the wettest period. Water table levels are generally being depressed. Vegetation is restricted and consists mainly of creosote bush, cacti and sage brush on the deserts, and mesquite, pinon juniper and various types of grass on the steppes. Precipitation varies from about 3 in. on the warm deserts to about 12 in. on the steppes. Most of this falls in the summer or winter, with only rare storms in other seasons. Summer thunderstorms, often accompanied by hail, bring cloudbursts which send torrents of water streaming down the mountains onto

Jan 1, 1964

By C. G. Dunn, M. Sharp

IN twinned crystals of the face-centered cubic metals the lattice of one twin is a mirror image of the other in a common twin boundary. When several twins appear within large grain in a sheet specimen, the twin one boundaries form a set of lines at the surface of the specimen which coincide with (111) planes of the large grain. Furthermore, for twins of the same orientation, these lines are parallel. Generally, the presence of identically oriented regions with straight parallel boundaries coinciding with a (111) plane of the surrounding crystal is strong evidence for identifying the island regions as twins of the parent crystal. However, Fig. 1, which shows the macrostructure of a large grain of copper with island regions that satisfy these conditions. is not an illustration of (111) twins. Since the reverse side of the specimen has much the same appearance, it was thought at first that these regions, which appear dark in the macrograph, actually were twins. According to X-ray data, however, these regions are second-order twins of the large crystal. With regard to their formation, these second-order twins formed by secondary recrystallization in a cube texture matrix. Growth occurred in the direction of the arrow (see Fig. 1) as the specimen moved slowly into a gradient temperature furnace as described previously.' Nucleation of the second-order twins occurred, therefore, on the ends facing opposite the arrow. If the origin of the second-order twins were due to repeated twinning, some first-order twin structure should be visible on these ends. This proved to be the case, as very small twins were readily found with the aid of a microscope, and probably could have been seen, in some instances, under ideal lighting conditions without aid of a microscope. Fig. 2 shows a cross-section view taken perpendicular to both the surface and the (111) trace of the parent crystal (visible as a straight boundary in Fig. 1) at the beginning point of growth of a second-order twin and where one first-order twin was relatively thick. In the micrograph, A is the large parent grain; B is the first-order twin of A; and C, which is a first-order twin of B; is a second-order twin of A. Between A and B and between B and C the major straight portions are traces of common (111) twin boundaries. The straight portion of boundary between A and C, however, is not a common crystallographic plane to the two lattices; it is a (111) plane of A and a (115) plane of C. Without considering the mechanism of twinning itself, the origin of the second-order twins may be accounted for in terms of repeated twinning and special growth characteristics. After each nucleation, a selective growth process can be thought of as favoring growth of the first-order twin in local spots only and favoring growth of the second-order twin to an extent comparable with that of the parent grain over relatively large areas in a way similar to that described for twinning in aluminum.' It has already been pointed out that the boundary between the large grain (A) and the second-order twin (C), which is responsible for the straight boundary portions in Fig. 1, involves a (111) plane of A and a (115) plane of C. The same combination of planes is not only possible in first-order twins, but actually appears quite frequently.3 Their prevalence in first-order twins and their presence here in second-order twins, together with the necessary occurrence of a large number of common lattice sites at the boundary, is an indication that this combination produces an "energy cusp"' boundary. (Energy cusp boundaries have been described by Shockley and Read.") The configuration of atoms near a {Ill), (115) boundary in first-order twins is of course different from the configuration near the same type of boundary in second-order twins. References 1 M. Sharp and C. G. Dunn: Secondary Recrystallization Texture in Copper. Journal of Metals (January 1952) Trans. AIME, p. 42. 2W. G. Burgers and W. May: Stimulated Crystals and Twinning in Recrystallized Aluminum. Recueil des travaux chimiques des Pays-Bas (1945) 64, p. 5. aD. Whitwham, M. Mouflard, and P. Lacombe: Discussion of W. C. Ellis and R. G. Treuting, "Atomic Relationships in the Cubic Twinned State." Trans. AIME (1951) 191, p. 1070; Journal of Metals (October 1951). 4 W. Shockley and W. T. Read: Dislocation Models of Crystal Grain Boundaries. Physical Review (1950) 78, p. 275.

Jan 1, 1953

Jan 1, 1923

By John W. Lane, Richard A. Ronzio, Frederick N. Bender

Climax Molybdenum Co. operated a hydrometallurgical plant at Climax, Colo., from August 1966 to August 1968 to recover molybdenum from an oxidized ore. The feed, tailings from sulfide flotation, was first upgraded by cycloning. The concentration plant handled 6000 tpd of feed and produced 2000 tpd of slime concentrate. The concentrate was leached by a sulfuric-sulfurous acid solution at 65°C. The molybdenum was solubilized in the form of "molybdenum blue." Activated charcoal was added to the leach tailings in a resin-in-pulp type circuit. Molybdenum was adsorbed on the charcoal. The charcoal was screened from the pulp and washed. The washed charcoal was pumped to columns where it was ammoniated and air-blown. The oxidized molybdate then was washed from the charcoal. The eluate was evaporated until ammonium dimolybdate crystallized out. The ammonium dimolybdate was calcined to molybdenum trioxide.

Jan 1, 1973

By Robert Abbott

THE influence of various elements in retarding or accelerating the absorption of carbon during the process of carburization is fairly well known. In general those elements which forth carbides accelerate the absorption, while those which do not retard it. It has sometimes been wrongly stated that those elements which raise the temperature of the critical range increase the absorption, while those which lower this temperature decrease it. Silicon is a notable exception to this rule, for its influence is to raise the critical range but to lower the absorption of carbon. Some elements which do not form carbides have no apparent influence upon the absorption rate. Carbon itself retards the absorption rate. With a view to obtaining more exact data upon the subject the following experiments were undertaken : 208 steels of different chemical composition were selected to represent most of the types of modern constructional steels. Specimens 3 in. in diameter and in. in length were weighed to milligrams. They were then packed in the special carburizing box shown in Fig. 1, and kept in .the furnace for 10 hours at a temperature of 900° C. A duplicate experiment was conducted at 1,000° C. At equal' intervals of time the box was rotated in the furnace so that. two complete revolutions were made in the 10 hours. This precaution was taken to neutralize as much as possible any effect of unequal heating. At the end of the 10 hours the box was allowed to cool in the furnace with the doors open. The specimens were then weighed again and the increased weight (carbon) determined. In. the following table are given the analyses of the various steels, together with the. increased weight of .carbon expressed in milligrams.

Jan 10, 1913

By D. B. Robinson, J. Lukacs

A knowledge of the equilibrium water content of hydrocarbon systems under pressure is important to the natural gas industry. The information available on the solubility of water in hydrocarbon, hydrogen sulfide, and carbon dioxide systems is reviewed in this paper and the influence of the more important variables such as temperature, pressure and molecular structure on solubility in liquids and gases is discussed. A suitable cbromatographic technique has been developed for determining low concentrations of water. Tailing of the water peaks has been elim inated by adding water to the carrier gas stream The method is applicable for both gas or liquid samples and is effective in the presence of hydrogen sulfide. The experimental study of water solubility in methane-hydrogen sulfide systems at a temperature of 16oF has shown that the presence of hydrogen sulfide causes only a modest increase in water content at pressures up to 1,400 psia. Theoretical considerations and data on pure hydrogen sulfide and carbon dioxide suggest that the effect of both these compounds will be greater at higher pressures and in the liquid phase. INTRODUCTION Before transporting or processing natural gases and gas condensates, it is usually necessary to dry them using suitable dehydration equipment. The design and operation of this equipment requires a knowledge of the amount of water present in the fluid at the reservoir and operating conditions. This is influenced by temperature, pressure and composition, particular1y when certain non-hydrocarbon components are present. Field experience indicates that hydrogen sulfide and carbon dioxide, for example, alter the usual water solubility relationships appreciably. However, an extensive search of the literature does not reveal any quantitative data on such systems. For sweet natural gases, generalized empirical correlations such as the one proposed by Katz, et al,6 can be used to predict water solubility with confidence at most temperatures and pressures of interest. However, existing theoretical relationships do not permit a calculation of the deviation from these curves when polar substances like hydrogen sulfide are present in the system. Thus one must resort to an experimental approach to obtain the necessary information. The fact that laboratory experimental methods frequently involve the use of mercury which reacts with hydrogen sulfide in the presence of water, and that hydrogen sulfide interferes with many chemical reactions specific for water has contributed to the difficulty of studying water solubility in systems containing hydrogen sulfide. In this investigation the water content of a limited member of methane-hydrogen sulfide mixtures was determined using a special technique with gas chromatography. REVIEW OF PUBLISHED DATA Experimentally determined water solubility data have been reported for methane, 14 ethane, 15 propane, 9 n-butane, 16 1-butene, 11 hydrogen sulfide 18 and carbon dioxide. 19 These studies report the effect of pressure, temperature and molecular structure on water solubility in single component gases and liquids. Fig. 1 compares experimentally determined water solubilities in several hydrocarbons, carbon dioxide and hydrogen sulfide at l00F as taken from this

Jan 1, 1923

By C. T. Eddy

The refining of native copper in the reverberatory furnace, as practiced in the Lake Superior district of Michigan, is very similar to the reverberatory melting and refining of cathodes, but the presence of arsenic in some of the copper concentrates renders the operation somewhat more difficult. Though the copper occurs as the native metal, which is often excep tionally pure—purer, in fact, than after it has undergone refining—its intimate association with the gangue minerals necessitates the cumbersome reverberatory treatment. The gangue consists chiefly of complex silicates of calcium, magnesium, iron, aluminum and sodium, but in certain ore deposits other minerals are often found, among them the native copper arsenides—mohawkite, whitneyite, algodonite and the like. These latter minerals, when present, because of their relatively high specific gravity (7.5 to 8.5), find their way into the concentrates through the gravity concentration processes employed in the recovery of the copper. When such concentrates are melted, the silicates are removed as slag, but, because of the great affinity of molten copper for arsenic, the arsenides dissolve more or less completely in the copper bath. Because of the stability of the resulting melt, the arsenic is tenaciously held in solution. The influence of arsenic on the properties of copper, especially on its electrical conductivity, is generally recognized. For certain uses it is beneficial, and in many instances its presence in limited amounts is not objectionable, but if the metal is to be used for electrical purposes, the almost complete removal of the arsenic is of prime importance. Considerable research has been done on the subject of the influence of arsenic on the electrical conductivity of copperll but the conclusions presented in the literature dealing with the problem show some disagreement. The methods now in use for the removal of arsenic have not

Jan 1, 1931