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It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori' molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,' using the data of Parravano and Malquori.' Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956

By B. J. Harlan

THE trying times experienced by the steel industry during the past four years have emphasized the necessity of producing pig iron at the lowest possible cost. The trend in both design and operation of blast furnaces has been toward this end rather than securing maximum production from a unit or group of units. In the following discussion the trend in design of stacks and auxiliary equipment will be taken up before operation is considered. Although few furnaces have been constructed in the past few years, the trend is definitely toward larger furnaces with a hearth diameter of 24 or 25 ft. Such a furnace is very flexible, being able to produce efficiently any desired daily tonnage between 500 and 1000 or more. The detail of the design of furnace stacks, with the exception of the top, has changed little in recent years.

Jan 1, 1934

By M. R. Tek, F. H. Poettmann, M. L. Grove

The general problem of single-phase natural gas flow through porous media has been considered both by mathematical analysis and field experiments. Theoretical studies on the fluid dynamics of natural gas wells resulted in derivations of expressions which permit a ber-ter understanding of the flow mechanism for conditions under which Darcy's law is no longer valid. In applying these results to natural gas production and testing technology, special emphasis war placed on the study of low permeability, slowly stabilizing formations. These applications resulted in a method of predicting the performance coefficients of tight natural gas wells. The calculation of the performance coefficient requires the determination of the "test-index", pkh/µ, the drain- age radius, R, and the effective wellbore radius, rw. Methods for estimating these parameters from field data were also developed. Field data from 15 wells were collected and analyzed. The measured values of the performance coefficients were compared with the predicted values. This statistical evaluation gave a bias of 7.14 per cent and a standard deviation of 11.6 per cent. INTRODUCTION The performance of a natural gas well is determined by the physical properties of the reservoir rock, the extent and the geometry of the drainage area, the properties of the flowing fluid, and the conditions of pressure distribution within the drainage matrix. The relation between the quantity of gas delivered and the pressure drop within the reservoir is characteristic of the behavior of each well and is often referred to as the back-pressure behavior of the well. It is well established that for normal, single-phase gas wells the relationship between the gas delivery rates and the bottom-hole pressure take, in general, the form, Q = c(P3 8 -P2 1)n. ,.......(1) where C is the performance coefficient, and n is the exponent corresponding to the slope of the straight-line relationship between Q and (P2 s, — P2 l) plotted on logarithmic coordinates. The determination of a well's performance by the back-pressure behavior not only permits the production engineers to analyze many operating problems, but also provides necessary information useful and essential to predict the future development of the field.' Important engineering and production problems such as calculation of gas deliverability into a pipeline at a predetermined line pressure, design and analysis of gas-gathering lines, determinations of spacing and number of wells to be drilled during field development to meet future market or contract obligations, etc., all depend, at least in part, on the availability and use of reliable back-pressure curves.' In the past the behavior of gas wells was evaluated

Jan 1, 1958

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 A. R. Elsea, C. C. McBride

HIGH-TEMPERATURE alloys, that is, alloys that are strong at high temperatures, have become increasingly important with the development of modern aircraft engines. Many alloys of this type are available. However, metallurgists do not have a clear understanding of the phases or structures which are responsible for these high-temperature properties. If these basic factors were understood, it might be possible to make better or cheaper alloys for service at high temperatures. For this reason, an investigation of the fundamental factors promoting high-temperature strength in alloys was started at Battelle Memorial Institute. This was to have included a study of the relationship between the structure and properties of cobalt-chromium base alloys of the vitallium type. It soon became clear that the structure of vitallium is quite complex and that the equilibrium diagrams which should explain these structures were unreliable. As a result, the cobalt-chromium binary diagram was determined as the first phase of this investigation1. This diagram is shown in fig. 1. During the study of the cobalt-chromium binary system, it was learned that these alloys may pick up considerable nitrogen when melted and heat treated in air. The extent to which nitrogen affects the various reactions in cobalt-chromium base alloys was not known, but there were indications that this impurity might be responsible for some of the erratic test results obtained for vitallium. Consequently, nitrogen was the first ternary addition studied. Thereafter the work was extended to ternary additions of iron and of nickel. This paper describes the investigation of the effects of nitrogen, iron, and nickel upon the reactions in cobalt-chromium alloys with 80:20 and 68:32 cobalt-chromium ratios. Experimental Work Alloy Preparation: A series of cobalt-chromium base alloys containing various amounts of the third element being studied were made for both the 80:20 and the 68:32 cobalt-chromium ratios. Electrolytic chromium, cobalt, and iron, and reagent-grade nickel powder were used as melting stock. Table I contains the chemical analyses of these materials. The charges were melted in alun-dum thimble crucibles which absorbed chromium oxide and effectively deoxidized the melts. These crucibles were supported by close-fitting graphite sleeves so that if they cracked during melting the metal would not be lost. Carbon increases, during

Jan 1, 1951

By Norman Carmichael, John Kiddie

The problem of transportation in the Clifton-Morenci district of Arizona has been one of peculiar difficulty and consequently has been an important factor in the cost of mining and treating the ores produced. From the crude beginning made over 50 years ago, many changes have been necessary to keep pace with the increased output of copper. A heavy-duty haulage system has developed on the original 20-in. track gage to meet the existent metal-mine conditions. Topography The transportation difficulties of this district may be readily appreciated from the relief map shown in Fig. 1. The northern half of the district is high mountainous country and there is a general but irregular drop toward the southern part, where the country, although still rugged, is in reality a great sloping plain. This is cut by numerous ravines from which the waters, in the rainy season, discharge into the channel of the San Francisco River. A chasm, 1000 ft. deep, has been eroded through the center of the district by Chase Creek, which is flanked by high irregular mountain masses, notably Copper Mountain, American Mountain, Coronado Mountain, and Markeen Mountain. The latter rises 2300 ft. above the bed of the creek, The San Francisco River has also cut a deep channel, though it is somewhat broader than Chase Creek. Eagle Creek traverses the extreme southwest portion of the area, where it has carved picturesquely through vast volcanic flows. Faulting has left its mark upon the topography of the district by adding to the irregularities caused by erosion. Strong faults occur at the Coro-

Jan 1, 1924

By Anderson, Burton E.

FOR several centuries diamond mining has been an adventurous, profitable and enticing industry in Brazil. Some of the world's most valuable diamonds have been found in this country. Two of the most famous stones are the "Estrella do Sul" (Southern Star), weighing 2541/ karats, and the "Branganca," weighing 1680 karats in the rough and 367 karats cut. For a great number of years the stones extracted and sold were mostly the white diamonds used for jewelry. Within the last thirty years black diamonds have been developed as an abrasive cutting material and in these black diamonds the State of Bahia, Brazil, has a monopoly of the world supply. Carbons, as they are commonly called, are being used for core-drilling, polishing, cutting, wire-drawing, and vari-ous other applications in which such a hard substance is required. Bernard Bandler & Sons, of New York City, have selected, graded and delivered these carbons to the United States markets.

Jan 1, 1932

By Bryon W. Cheever

The greatest objection to be brought against the present methods for estimating phosphorus in iron and steel, is the time consumed in the operation. The following method, originated and perfected by Mr. E. D. Campbell, assistant in the chemical laboratory of the University of Michigan, will, 1 think, if carefully followed out, give results that are sufficiently accurate for technical purposes, and will give them in less time than they can be obtained by any other process. The process consists in comparing the color obtained by the action of stannous chloride upon a solution of the phospho-molybdate precipitate obtained from the solution of iron or steel, with that obtained from a standard solution of molybdie acid which represents a given amount of phosphorus. The operation is as follows : Take of ordinary steel 1 grm. and treat as in any of the wellknown processes until the phosphorus is precipitated as ammoniumphospho-molybdate. When precipitated, the phospho-molybdate precipitate is filtered out, thoroughly washed with an acid solution of ammonium nitrate, and, finally, twice with water, to remove most of the ammonium nitrate. The precipitate is then dissolved in about 1 c. c. of 10 per cent. potassium hydrate, which is let fall drop by drop on the filter till the precipitate is dissolved ; the filter is now washed with about 25 or 30 c. c. of water, and the potassium hydrate solution, which now consists of 25-32 c. c. of solution, is boiled until the peculiar frothy appearance, which first appears on boiling, is entirely gone. The solution is then cooled until perfectly cold, and about 10 or 15 c. c. of strong hydrochloric acid added ; if the solution is kept cold this will form no precipitate, but a light yellow or colorless solution. The solution is now ready for the addition of stannous chloride, and the subsequent comparison of color produced with that obtained from the standard molybdie acid. The comparison is made in tubes that are calibrated like carbon-tubes, but which are larger, about 5/8-inch bore, and graduated to 100 c. c.; this makes them about 18 inches long. To make the comparison of color, first transfer the now acid solu

Jan 1, 1886

By J. H. Scaff, H. C. Theuerer

Germanium may be reversibly converted from n to p type by heat treatment. Data for the conversion and the associated changes in resistreatment.tivity are given and the results are interpreted in terms of changes in the donor-acceptor balance. MEANS for controlling the electrical properties of germanium in a predictable manner are of interest because of the increasing utilization of this element as the semiconducting material in electrical devices. Since both the mechanism and the magnitude of the electrical conductivity depend upon the kind and quantity of impurities present, the conductivity usually is adjusted by first carefully purifying the germanium, and then, by standard alloying procedures, adding the elements desired. The elements usually added are from the third or fifth periodic groups depending upon whether p- or n-type germanium is desired. However, in the development of germanium rectifiers during the war, it was found that it was possible also to modify reversibly the conductivity of germanium and even to produce conversion from n to p type by heat treatment.1,5 Since then a detailed study of this effect has been made. The data are presented in this paper and an explanation is offered for the effects observed. Preparation and Experimental Procedure The method used in preparing the germanium ingots for this investigation has been previously described.' The method consists essentially of (1) reduction of GeO2* and (2) preparation of a 50-g ingot from the reduced material. Graphite containers are used in both steps. In the first step the GeO2 is reduced in hydrogen at 650 °C to form a sponge germanium which, to assure complete reduction and to obtain massive materials, is fused subsequently in the reduction furnace by gradually raising the temperature to 1000°C. The button of germanium thus obtained corresponds to a yield of 99.8 pct. The final ingot is prepared by fusion of the germanium button in a helium atmosphere. A cylindrical crucible in a vertical silica tube furnace is employed and the crucible is heated by an external induction coil. The ingot is solidified from the bottom upward by raising the induction coil at a constant rate with power to the coil kept at a fixed value. In such ingots, segregation is normal and most of the impurities are concentrated in the last region of the ingot to freeze. It follows then that the major portion of the ingot is purer than it would have been if freezing had occurred in a random fashion. Moreover the orderly advance of the freezing surface during solidification establishes in the ingot a succession of surfaces of constant composition, if it is assumed that the liquid is homogeneous and that diffusion in the solid is negligible. Therefore, some information on the distribution of impurities in the ingot may be acquired by determining the shape of the solid-liquid interface at different stages of solidification. This is of importance because the concentration of impurities will be seen to affect the response of germanium to heat treatment. Such information is difficult to acquire by direct means, for the impurities responsible for the electrical properties of germanium prepared in this way are present

Jan 1, 1952

H. 0. Hofman, Boston, Mass. (communication to the Secretary*) :—The experimental demonstration by Professor H. Ries, of the fact that a mixture of clay and finely-ground flux will melt more readily than one in which the flux is less fine and therefore less intimately mixed, is very striking, and will be appreciated especially by those who have to discuss, before classes of students, fusions on a small or a large scale. The statement, that I " rather disputed" the influence of size of flux-particles on the ease with which fire-clay mixtures fused, is an erroneous inference from the paper written by Mr. B. Stoughton and myself in 1898.' We did not undertake to study the influence upon fusibility of the sizes of the particles, either of clay or flux. What we did try to find out was, whether the common practice of finely grinding raw or burnt clay, or a mixture of the two, before testing with Seger cones for resistance to heat and to fluxes, xould give the same results as if the materials were tested just as they were going to be

Jan 1, 1904

By J. P. Sheeha, W. F. Craig, M. Baeyertz

The loss in toughness caused by phosphorus within commercial ranges was studied in AISI-SAE 1340 steel and in molybdenum modifications of this grade. The replacement of part of the manganese by molybdenum in amounts which maintain the hardenability of the standard 1340 grade was shown to counteract to a marked degree the detrimental effects of phosphorus. THIS paper deals with the effect of phosphorus on the toughness of 1340 steel and with the effect on toughness of replacing part of the manganese by molybdenum while retaining the same hardenability as that of 1340. In previous work1 a progressive decrease in toughness was observed when the phosphorus content of 5140 was raised from 0.020 to 0.036 pct; that is, from a moderate phosphorus level to one higher but yet within the AISI-SAE specification for this grade. The structural condition of the steel was tempered martensite. Toughness was evaluated by the transition temperature determined by V-notch Charpy tests. Replacement of a part of the chromium in 5140 by molybdenum provided a factor of safety against loss of toughness caused by phosphorus, especially where the steel was cooled slowly after tempering. Scope of the Study: In view of the improved tolerance for phosphorus obtained by replacing a part of the chromium in 5140 with molybdenum, it seemed desirable to investigate the possibility of obtaining similar improvement in 1340 by replacing part of the manganese with molybdenum. Heats were made at different phosphorus levels, in a series that began with 1340 and ended with steels containing 0.32 to 0.35 pct Mo with 0.82 and 0.90 pct Mn. The analyses of the heats are given in table I. In order to facilitate later discussion, the 1340 heats have been placed together in the order of increasing phosphorus content, and the molybdenum modifications have been grouped according to phosphorus

Jan 1, 1951

By Elburt F. Osborn

The phrase "Clean Synthetic Fluid Fuels From Coal," implies that it is possible to obtain adequate and dependable supplies of fuel without sacrificing the quality of our air, water, and land. Because of the long lead times needed to develop technical feasibility, into commercial reality, however, vigorous efforts must be made now in order to do it. The available options for clean fuels include many exotic sources, like solar and geothermal power, fuel cells, and thermionic and thermoelectric systems. To solve the energy crisis, however, we have three basic energy criteria-abundance, reliability, and commercial availability by 1985. Only processes based on converting coal and oil shale to clean, synthetic fluid fuels can meet all three.

Jan 9, 1974

By James E. York

THE honor so fairly earned and so incompletely and tardily paid to Henry Cort, the inventor of the puddling-furnace and the, rolling-mill, has been fully set forth by Mr. Charles H. Morgan,1 and needs no further emphasis here. In view of the importance of the rolling-mill in the treatment of iron and steel, the paucity of information concerning it is surprising. With the exception of a hook, written about 35 years ago, by Peter Bitter von Tunner, an Honorary Member of this Institute, and of desultory articles on simple sections, which have appeared in technical journals, I know of no pub¬lication attempting to treat this subject, although volumes have been written on the scientific theory and technical manipulations involved in other branches of the iron- and steel-industry. This strange anomaly may be due to the fact that roll-turning cannot be called a scientific business. It does not ordinarily come within the range of an educated engineer; yet it cannot be performed by an ordinary mechanic. It demands some of the qualifications of an engineer, in designing, and those of a mechanic, in execution. The men who have followed this trade have controlled the training of their successors. In many cases the technical knowledge required bas been handed down from father to son, and there has been a motive of private interest to prevent its public dissemination. Moreover, the statement of the various principles involved in the process would require, besides manual experience, a degree of scientific knowledge which roll-turners do not usually possess; and, finally, any book on the subject, in order to possess real, practical value, would have to be so fully illustrated as to make it very costly to publish. Regarding my own experience, I may say that I served a six-

May 1, 1906

By Edwin Chance

DURING the past 10 years, the safe and efficient lighting of the coal mines of this country has received an ever-increasing amount of attention. Several States have passed laws attempting to regulate the type of lamp to be used and the nature of the fuel to be burned, and the mining departments of coal-mining States have generally shown a keen and intelligent interest in this subject. The passage of the recent Employers' Liability Act in Pennsylvania has made it necessary for many coal-mining companies to take out liability insurance, and the companies underwriting such insurance have made it desirable for the insured to permit the use of, none but illuminants of established worth. While these conditions have not obtained for a sufficient length of time to permit the statement that the illumination of coal mines by portable lamps has been standardized, still, considerable progress has been made and the direction of future practice in this branch of coal-mining technology is very evident. Under these conditions it seemed that a review of the methods now used in coal-mine illumination, together, with a brief consideration of the principles underlying these methods, might be of some interest. Miners' lamps may be divided into three classes: The open light, the electric cap lamp and the flame safety lamp. It will be desirable to consider each of these classes separately, as each has properties peculiar to itself and one class is hardly comparable with another. In this country, without question, the open light is the most generally used of all miners' lamps. This fact is explained by the relative freedom of a large proportion of our mines from gaseous conditions, and by the admirable systems of ventilation installed in those that show a tendency toward such conditions. In the metal relines, the miner's candle has had and still has considerable vogue. Because of the small amount of ventilation usually supplied in metal mines, the freedom of the candle from any tendency to produce noxious gases or offensive odors, and the small amount of air it consumes, are. valuable assets, while, because

Jan 2, 1917

By G. S. Cole, G. F. Bolling

Recent experitnents on crystal growth have indicated that thermal convection in the liquid influences the conditions of solidification and subsequent crystal characteristics. However, the important columnar-equiaxed transition in castings has not been examined as a function of this free convection. An experiment is presented here to demonstrate a change in the transition as convection is suppressed. Lead- and tin-based alloys were cast in stainless-steel molds either without special procedures or with thin grids placed horizontally across the tnold diameter in portions of the castings. While the grids allowed some diffusion of heat and mass transport to occur during solidification, massive fluid flow was hindered in the vegiotz of the grids. A larger percentage of columnar grains appeared in the grid region than in other parts of the special castings or than in all regions of normal castings. This structural difference can be explained in terms of thermal convection. THERE is little information about the possible effects of natural convection which may occur during the solidification of a casting. Ruddlel-3 has stated that the movement of liquid metal produced by convection might assist in the transfer of heat, but in the absence of confirmatory evidence he suggested that this idea be treated with caution. chalmers4 considers, but does not assess, the importance of fluid motion in casting, while Tiller5 suggests that, in liquid metals which have extremely high thermal diffusivities, the effects of thermal convection may be negligible. In addition, throughout the literature, there are statements indicating the possible presence of thermal convection but without proofs or evaluations of its influence. Natural convection may be divided into two categories: thermal convection, where liquid flow is due to density differences caused by temperature gradients in the liquid (e.g., liquid near a cold wall falling with respect to hotter liquid further away from the wall); and solute convection, where flow is due to density differences as a result of concentration gradients, see Wagner.6 In most instances thermal convection predominates over solute convection. Nevertheless, even thermal convection has not been studied in any detail and is difficult to handle, since it can vary quantitatively from one experiment to another depending upon the exact positions of heat sources and sinks or the attitude of the container with respect to gravity. In spite of these difficulties it is possible to realize that a higher rate of heat transfer must result with convection than in any situation where conduction acts alone. Thus, the degree of increased heat transfer is the important undecided question in considerations of casting. It will be demonstrated here that a reduction in convective flow leads to a suppression of the columnar-equiaxed transition in a casting and that this suppression is related to a decrease in the degree of heat transfer. Fortunately it is possible to do this by comparative rather than quantitative measures. The insertion of horizontal plates or grids into a simple mold does not appreciably influence heat transfer per se, but in reducing the allowable height through which colder liquid may fall freely it reduces natural thermal convection. This leads to a reduced fluid velocity, a different flow pattern, and an altered heat transfer which can be measured. EXPERIMENTS The alloys were prepared from elements of 99.9 pct nominal purity and cast into an uncoated 2-in.-diameter stainless-steel mold insulated at the bottom with a suitable refractory so as to ensure predominantly radial heat flow during freezing. Casting was performed either in empty molds or in molds containing grids or plates in various configurations . The grids were constructed of aluminum screen (1/32 in. thick) which was cut to the desired shape, cleaned in aqua regia, and coated with a mixture of 2 parts aqua dag graphite -1 part Sauereisen cement mixture, thus supplying a hard, protective, and insulating layer approximately 0.006 in. thick. The

Jan 1, 1965

By Rossiter W. Raymond

The most important event in the history of mining in the United States was the discovery of gold in California, which led to the rapid development, not only of a new industry, but of a new empire. The settlement of the Pacific slope was making but slow progress under the inducements of a scanty commerce in furs and hides. The liberal grants offered by the government to agricultural pioneers in Oregon had attracted to the Willamette valley and other favored points in that territory a limited population; hot the government of the Mexicans in California was positively unfavorable to enterprise. It is true that gold was known to exist in the country. Rumors of it were current among the trappers, and placers had actually been worked in what is now Los Angeles County; but the padres of the neighboring mission of San Fernando had discouraged the business as demoralizing to their flocks; and the existence of the precious metal was not widely known; still less was its distribution northward suspected. The discovery of gold, January 19th) 1848, at Sutter's saw-mill, on the south fork of the American River, afterward famous as Coloma, in Eldorado County, was the beginning of the new epoch. This discovery was made by James Wilson Marshall, a partner in the mill, who observed in the debris washed down by the tail-race a glittering fragment of a mineral unknown to him. Suspecting it to be gold, he sought for further specimens, and obtained, in the course of a few days, several ounces of it. Tests subsequently

By K. K. Clark, W. H. Somerton

The feasibility of reducing pressures needed to fracture formations by heating the borehole intensively has been investigated on a laboratory scale. Reductions in fracture pressures of heated Bandera, Berea and Boise sandstone cores were observed at various confining pressures, simulating reservoir stress conditions to a depth of 5,000 ft. Both permeable and impermeable borehole boundary conditions were tested. Three heating conditions were used in the tests. One group of samples was heated in a furnace to a temperature of 600C, cooled to room temperature., and then tested for fracture pressures. Two other groups of samples were heated with a borehole heater to maximum borehole wall temperatures of 625 and 792C, then cooled and tested. In all cases, heated samples showed substantial reductions in fracture pressures compared to unheated samples. The higher temperature borehole heated samples showed the greatest reduction, amounting to 70 per cent in the extreme case. In actual application to wells, it was concluded that fracture pressures may be reduced by 20 to 50 per cent by intensive borehole heating before fracturing. INTRODUCTION Hydraulic fracturing of oil and gas wells is an accepted and effective technique for increasing well productivity in many areas, but is notoriously unsuccessful in other areas. The technique becomes less interesting for production stimulation purposes when excessive fracture pressures are necessary. Formations which do fracture but require high pressures, probably form horizontal fractures. There is good evidence to indicate that some formations do not fracture at all, but yield plastically under high pressure. Thus, any technique which will make formations easier to fracture or will reduce fracture pressures is potentially interesting to petroleum producers. Horizontal fractures generally occur in planes of weakness, such as bedding planes, and at pressures equaling or exceeding the effective overburden stress. In the unusual case where planes of weakness do not exist, a slightly higher pressure must be applied to overcome the tensile strength of the rock. In general, high fluid-loss fracturing fluids are conducive to the formation of horizontal fractures.1 Vertical fractures, when they do occur, are initiated at pressures generally lower than overburden pressure and are favored by low fluid-loss fracturing fluids or impermeable boreholes. The pressure necessary to create a vertical fracture in an impermeable, elastic medium can be predicted from the so-called "thick-walled cylinder" equation: Pf = 2 or+ st.............(1) where pf = fracture pressure or = radial stress st = tensile strength of medium. This equation indicates that to fracture it is necessary to overcome a tangential compressive stress, induced by and equal to two times the radial confining stress, plus the tensile strength of the medium. If the above equation held strictly true for rocks, very little could be done to reduce fracture pressure. The tensile strength of the rock might be reduced somewhat, but any change in st would be small compared to the magnitude of the tangential stress at reasonable subsurface depths. Laboratory tests have shown that actual fracture pressures exceed values predicted from Eq. 1 by factors of 1.4 to 28.6.1,2 Eq. 1 thus does not properly describe the

Jan 1, 1966

By H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe's formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade's exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965

By Jesse O. Betterton

In the Parkes process of lead refining, after desilverization has been completed by means of zinc additions, there will remain in the lead from 0.5 to 0.6 per cent zinc. At this stage in the refining practically all impurities are reduced to refined lead specifications except zinc and antimony. All excess of copper and nearly all the arsenic goes out with the silver. Silver remaining should not exceed 0.1 oz. per ton. It thus remains only to remove zinc and antimony to produce refined lead. The older practice was to complete refining by means of oxidation processes in reverberatory furnaces. Essentially this consisted of heating the lead to 1200' to 1300" I?. and allowing it to come in contact with a considerable excess of air passing through the furnace, or accomplish the same result by blowing the lead with steam by means of pipes introduced for that purpose, at the same time allowing air to enter the furnace. Usually some procedure involving alternate oxidation and reduction with fine coal or coke was employed in order to reduce the weight of dross or skim finally removed from the furnace. This practice had many elements of weakness in that the main flour of lead, after the preceding expensive operations had been performed, and the whole refining process nearly completed, was subjected to an operation at a comparatively high temperature, which involved much lead loss if the furnaces were not on bags, and the production of 3 to 5 per cent of the weight of the lead as dross or skim, which had to be resmelted and the lead either refined or produced as antimonial lead. In addition, the operating expense of the process was a considerable item. The process of dezincing with chlorine was developed as a substitute for the foregoing described oxidation process, and finally resulted in such advantages as nearly equal operating costs, a practical elimination of the lead loss, and the direct production of a very valuable byproduct, zinc chloride, that may be sold as such or retreated for its zinc and chlorine contents, both of which can be reused in the refining processes. Essentially this process consists of circulating the lead by means of a pump in a kettle through a closed reaction cylinder, gaseous chlorine entering the reaction cylinder with the stream of lead from the pump. Molten zinc chloride is thus produced and is discharged together with

Jan 1, 1937

By Richard G. Warren, Michael M. Minor, Gayle J. Thomas

INTRODUCTION Los Alamos Scientific Laboratory (LASL) initiated its effort in the Hydrogeochemical and Stream Sediment Reconnaissance (HSSR), a part of the Department of Energy (DOE) National Uranium Resource Evaluation (NURE) program, in late 1975. Since that time, LASL has completed sampling of the Rocky Mountain states of New Mexico, Colorado, Wyoming, and Montana at a density of about one water or waterborne sediment sample per 10 km2 and has sampled about 85% of Alaska at a density of at least one per 25 km2. Analytical results for these samples are reported by National Topographic Map Series (NTMS) quadrangle. All collection and analytical procedures have been standardized from the outset (Sharp, 1977; Sharp and Aamodt, 1978). Until early 1979, only uranium results were reported for these samples; thereafter, results include analyses for at least 42 additional elements in the sediment samples. Each LASL HSSR report also includes a discussion of the relationship of these analytical data to known or possible uranium resources; more recently, these data have been re- examined for their relationship to resources for other metals (Beyth et al., 1980; 1980a). Analytical results for LASL HSSR sediment samples are both comprehensive, including 43 elements, and precise, allowing close inter-comparison of data between quadrangles. A recent HSSR study shows that elemental concentrations in sediment samples from the Dixon Entrance quadrangle in Alaska are insensitive to the choice of sieve size fraction and do not vary significantly between stream locations a few meters apart, except for extremely high elemental concentrations (Warren, et al., 1980). Elements that are particularly reproducible include thorium, hafnium, and the .ram earth elements. Fortunately, sensitivities for these elements, which are often associated with uranium, are excellent by the nondestructive analytical technique of neutron activation analysis that LASL employs. Wet chemical techniques may not always give reliable results for these elements in sediment samples due to the difficulty of dissolving the resistate mineral phases that normally contain these elements. LASL has recently open-filed results for a large number of NTK3 quadrangles; to date analyses have been reported for about 605 of the quadrangles within the states of the Rocky Mountain region. As a result, uranium analyses am now complete for all sediment samples collected from the state of Wyoming. We have chosen to sumnarize the analytical results for Wyoming and portions of adjoining states hereafter termed "the ~ Wyoming regionn (Fig. 1 ) ; nearly 24 000 uranium analyses and nearly 17 000 analyses for 42 additional elements are available for sediment samples collected from this area. The DOE open-file report numbers are shown in Fig. 1 for reports open filed before September 1, 1980. The Wyoming region provides an ideal area for an examination of regional geochemical patterns ex- hibited by sediment samples. It is endowed with a variety of exposed geologic units and with widely distributed uranium districts associated with host units of several ages. However, discussion will focus on rock units of Eocene and Precambrian ages because they are widely exposed and host the majority of the uranium resources within the region (Fig. 2). Miocene units are also widespread and host mineralization in the Brown's Park Formation (Fig. 2). Epigenetic uranium mineralization occurs in sand- stones of lower Eocene age such as the Wasatch, Battle Springs, and Wind River Formations whereas vein type mineralization occurs in Precambrian crystalline rocks. Precambrian rocks within the region consist of a variety of granitic and meta- morphic rocks with l .4-2.8 billion year ages, except within the Uinta Arch, where they consist of a sequence of very low grade metamorphosed or unmetamorphosed 1.0 billion year old sedimentary rocks. Precambrian rocks have served as sources for much of the clastic material comprising the lower Eocene units, and may also have provided the source for the uranium in mineralized Eocene or Miocene sandstones (Stuckless, 1979). The remainder of this paper describes the relationship of elemental concentrations in HSSR sediment samples to exposures of Eocene and Precambrian rocks. The results are used primarily to determine where these Precambrian rocks might provide the most suitable uranium source areas and to infer the direction of transport toward adjacent depositional basins during the Eocene.

Jan 1, 1980