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By M. R. Geer, H. F. Yancey

Four coals were treated in the Humphreys spiral concentrator, and the products were examined by float-and-sink and screen-sizing tests to determine fundamental performance characteristics. The efficiency of the separation between coal and impurity was shown to be influenced greatly by particle size.

Jan 1, 1950

By Clyde Wyman

THERE has always been a question as to the extent to which oxidizable alloys might he recovered from charged scrap in the, acid electric furnace. While qualitative information was not lacking, the quantities that might be recovered and the conditions best suited for such recovery were not clearly defined. The present investigation was carried out to determine the efficiency of alloy recovery from residuals contained in the bath, especially in regard to the recovery of vanadium. A series of 24 heats was produced at the Burnside Steel Foundry Co., including medium manganese-molybdenum-vanadium, manganese-chromium, and grade B steels, in which vanadium recoveries from the residual vanadium were investigated. Recoveries of other alloys were also studied from the accumulated data. These heats were produced in a 5-ton acid-lined electric furnace. The analysis of metal and slag samples and the micrographs were prepared by the Research Laboratories of the Vanadium Corporation of America. In addition to the vanadium contained in the scrap charge, ferrovanadium was added to the charge and to the molten bath to bring the residuals up to the desired level. Vanadium pentoxide (V2O5) in one series of heats was added to the bath after meltdown, for the same reason. In addition to the general furnace practice, the slags of these various heats were treated with coke breeze, Ferrocarbo-S (silicon carbide), and aluminum dross to determine the effects of different reducing agents upon the alloy recoveries and upon the final product.

Jan 1, 1947

By Jos. Van Ackeren

Although the Siemens regenerator principle was introduced into byproduct coke-oven design about 40 years ago, many problems of construction, and particularly of heat distribution and pressure conditions, have not been fully solved. Heat should be applied to the walls of a coke oven in such a way that the coking of the charge of coal will be completed everywhere at the same time, and at approximately the same temperature. This means that the application of heat should be uniform from the top to the bottom of the coal mass (except for the thin layer at the top that is purposely kept at a somewhat lower temperature to reduce cracking of the byproducts); also that a little more heat must be applied to the coke end than to the pusher end, because the coal mass is a little thicker at that end. As a modern coke oven is about 40 ft. long and 12 ft. high, a real problem is involved in the proper application of heat to the oven walls so as to secure quick coking time (without endangering the walls through local overheating) and produce coke made at a uniform temperature. Design of Ovens In all regenerative ovens, the points of combustion are arranged in duplicate sets, one set operating in one-half the area of the heating wall and the other set alternately operating in the other half. Because of the reversal of the flow of gases, the points of maximum and minimum temperatures are alternately located at the same places, thus preventing dangerous local overheating. The practicability of the principle of reversal of flow seems to have been recognized at an early date, and has been applied with every conceivable flue arrangement, combustion chamber, and means of air and gas supply. To summarize the various principles that have proved useful for the control of oven-wall temperature, the best practice seems to have resulted from the acceptance of the use of vertical flues; the separate supply of air and gas to the base of these flues, with the resulting flame

Jan 1, 1923

By Jos. Van Ackeren

Although the Siemens regenerator principle was introduced into byproduct coke-oven design about 40 years ago, many problems of construction, and particularly of heat distribution and pressure conditions, have not been fully solved. Heat should be applied to the walls of a coke oven in such a way that the coking of the charge of coal will be completed everywhere at the same time, and at approximately the same temperature. This means that the application of heat should be uniform from the top to the bottom of the coal mass (except for the thin layer at the top that is purposely kept at a somewhat lower temperature to reduce cracking of the byproducts); also that a little more heat must be applied to the coke end than to the pusher end, because the coal mass is a little thicker at that end. As a modern coke oven is about 40 ft. long and 12 ft. high, a real problem is involved in the proper application of heat to the oven walls so as to secure quick coking time (without endangering the walls through local overheating) and produce coke made at a uniform temperature. Design of Ovens In all regenerative ovens, the points of combustion are arranged in duplicate sets, one set operating in one-half the area of the heating wall and the other set alternately operating in the other half. Because of the reversal of the flow of gases, the points of maximum and minimum temperatures are alternately located at the same places, thus preventing dangerous local overheating. The practicability of the principle of reversal of flow seems to have been recognized at an early date, and has been applied with every conceivable flue arrangement, combustion chamber, and means of air and gas supply. To summarize the various principles that have proved useful for the control of oven-wall temperature, the best practice seems to have resulted from the acceptance of the use of vertical flues; the separate supply of air and gas to the base of these flues, with the resulting flame

Jan 1, 1923

GENERAL GEOLOGICAL DESCRIPTION The uranium mineral appraisal herein described was made for an ore deposit in New Mexico. The uranium mineralization occurs as roughly tabular to lens-shaped deposits of varying thickness within the sandstone of the Jackpile formation of Jurassic age. The mineralization occurs at several horizons within the Jackpile formation, but is not always confined to specific beds. It often transgresses across stratigraphic layers, as demonstrated when attempting correlation of uranium gamma anomalies between adjacent drill holes. Preferred mineral trends have been established in some parts of the deposit, but are not always predictable when attempting to extrapolate beyond the zones defined by drill hole sampling. MANAGEMENT OF DRILL HOLE SAMPLE DATA All of the drill hole sample data used in the appraisal were obtained from interpretation of gamma-ray logs. A brief description of gamma-ray log sampling is given in Chapter 2. Two preliminary steps are involved in preparing gamma-ray logs into sample data normally acceptable for computer manipulation. 1) The gamma analog trace produced by the downhole probe must be digitized, i.e., counts-per-second (CPS) are recorded for each 0.15 m (1/2-ft) interval across the gamma-ray anomaly. The work is usually done on a "digitizer" while following the analog trace with an electronic stylus on a special tablet or table. The other alternative is to do the work manually. Some of the newest downhole logging equipment produces a magnetic tape output which can be read by a computer. 2) The gamma-ray CPS values must then be converted to equivalent U308 assay values, taking into consideration all appropriate correction factors. The US Atomic Energy Commission, now part of the Department of Energy, developed the theory and algorithm for this conversion in the 1960's, and though the work can be done manually, it is best done with the GAMRED (gamma-reduction) computer program. Fig. 14-1 illustrates a typical analog trace produced by the probe instrumentation, including gamma-ray trace (left), self-potential electric log (center), and resistivity log (right). Fig. 14-2 shows a form of the computer output after the analog data has been digitized to 0.15-m (1h-ft) intervals and converted to percentage U308 values for the same hole. The U308 grade bar graph on the right permits rapid visual inspection of anomalous values by depth and elevation. The converted U308 sample data were next processed by the SURVEY program that assigned to each assay interval [0. 15-m (1h-ft)] an X Y Z coordinate, taking into account all deviations indicated from downhole survey information. The output file of the SURVEY program was listed on the line printer for examination by project geologists, and also became the main input file for the URAN/ COMP compositing program, which is designed to group individual 0.15-m (/-ft) U308 sample values into larger intervals representing discrete anomalous zones according to a series of specified parameters entered into the program by the user. Composite U308 intervals were computed by the URAN/COMP computer program, the logic of which may be briefly described as follows: Step 1 The program searches for the highest U308 value in the hole and builds a composite by adding the highest grade interval on either side so long as the added value is greater than a minimum acceptable grade, and the total composite, after addition, meets minimum GT (grade times thickness) constraints. Step 2 The program loops back to find the next highest assay value in the hole not already included into a composite, until all anomalies above minimum cutoff grade are composited. Step 3 Individual composites are combined if they are closer than a specified minimum waste thickness, and the resultant composite grade still meets GT minimums.

Jan 1, 1980

By P. L. Weston, S. E. Khalafalla

A systematic study was made by the Bureau of Mines on the effect of so me hypothesized accelerators for the process of wustite reduction in carbon monoxide. When small concentrations of promoter materials in the order of 0.69 at. pct were added to the reducible charge, the rate of reduction to iron was increased. Promotion phenomenon prediction was made in light of a suyface reduction mechanism with the aid of Vol'kenshtein's effect regarding the propagation of crystal lattice disturbances by small amounts of relatively larger interstitial ions. The acceleration produced by a typical promotor, such as potassiunl, increases with protnoter concentration up to a maximum, beyond which the reduction rate decreases. Concentration for maximum promotion depends on the nature and physicochemical properties of the promoter. The extent of reduction rate enhancement is found to be directly proportional to the atomic volume and electronic charge of the additive. DESPITE the enormous volume of literature on iron oxide reduction, very little is reported concerning additive or impurity effects on this important metallurgical process. The beneficial effect bf calcium compound additions on the reducibility of iron oxide sinters has been reported by Tigerschiold,1 vor dem Esche,2 and Edstrom. Doi and Kasai~ found that the addition of lime or limestone to iron ores helps to break up any unreducible compounds, such as fayalite or ilmen-ite. and thus free the combined iron for reduction. Schenck et al. 5 suggested that the increased reduction rate obtained when adding lime could be accounted for by the instability of wustite in the presence of lime. Acid-base slagging reactions resulted in wustite disproportionation according to The dicalcium ferrite formed will yield iron and calcium oxide during reduction. Regenerated calcium oxide dissociates more wustite. This mechanism has been used by Seths and white7 to explain their experimental results. Recently, Strangway and ROSS' attributed the calcium carbonate acceleration of iron oxide agglomerate reduction to increased porosity, both initial as well as that developed during reduction. Aside from calcium carbonate, or oxide, no other promoter was noted in the literature, except for a brief mention by Barrett and woodg on the effect of sodium carbonate and aluminate as activators for the hydrogen reduction of magnetite at 600°C. The present investigation systematically studied a host of other promoters, including calcium and sodium, in an attempt to elucidate the mechanism by which promotion takes place and to fit the results into a simple chemical model. To attain this goal, the effect of promoter physical properties, such as atomic volume, electronic charge, and concentration are related to wustite reduction kinetics in this paper. Wustite reduction to iron, rather than the overall hematite reduction, was chosen since this reaction is known to be the slowest, and hence the rate-deter mining step for the overall iron oxide reduction process. EXPERIMENTAL PROCEDURE Raw Materials and Their Preparation. The pure or impregnated wustite pellets were prepared from minus 400-mesh chemically pure hematite powders. A known weight of hematite was thoroughly and uniformly mixed with a calculated weight of the additive. The mixed paste containing 35 wt pct water was gradually heated from 400" to 1200° C and fired at 1200°C for approximately 4 hr in an air atmosphere. After cooling, the sinter was pulverized to minus 100 mesh and pelletized into minus 4- plus 5-mesh spheres. Pellets were fired, similarly to the paste mix, air-cooled, sized, and stored. An appropriate weight of the charge (20 g) was placed in a zirconia reduction tube maintaining a uniform oxide bed height of 1 cm and a cross section of 7.1 sq cm for all of the test runs. The samples were supported in the vertical reaction tube by a bed of fragmented insulating firebrick plus 3- to 6-mesh alumina beads. The hematite was then transformed to wustite by reduction with a 30 pct CO2-70 pct CO gas mixture at 1000°C in a globar furnace. Complete conversion to wustite was ascertained by a continuous infrared gas analyzer recording the CO-CO2 content of the effluent gas until no carbon monoxide was absorbed from the inlet gas, and inlet-outlet gas analysis remained constant for 30 min. The wustite sample was then reduced with 100 pct CO at 100WC. From the recorded data, an initial rate of reduction was determined by the initial slope of the graph percent reduction vs time. In order to estimate the accuracy of the data, five separate determinations of the reduction curve of pure wustite, under otherwise identical conditions, were performed. The maximum deviation from the average reduction at 14 min amounted to 2 2 pct reduction. This deviation corresponds to 3.8 pct variation based on the percent reduction of the sample. Aiiy impurity effect below the limits of this maximum deviation was considered a spurious result. If the effect exceeded + 4 pct, then it was considered as a positive one. Considerable care was exercised in determining the initial rate from the slope of the initial segments of the curve. Each reduction curve was examined separately on large graph paper and the best tangent to the curve at zero time was drawn. The slope of this tangent was taken as a measure of the initial fractional reduction per minute. Although the time required to reach 50 pct reduction may be of special practical significance, initial rate measurements are invaluable in fundamental studies. These rates provide a measure of the process kinetics on the initial

Jan 1, 1968

By D. Mills, G. B. Craig

ZIRCONIUM has been float-zone-refined in an electron-beam furnace and the redistribution of oxygen, iron, and tungsten has been measured. The iodide zirconium used in the present experiments initially contained both oxygen and iron in the range 100 to 200 ppm by weight, and tungsten in amounts less than 10 ppm. Float-zone refining of zirconium, using induction heating, has previously been attempted by Kneip and Betterton1 and Langeron.2 Kneip and Betterton were primarily interested in the removal of iron and nickel. They achieved some purification, with respect to both these elements, in material given up to six passes at 150 mm per hr under an argon atmosphere. Langeron reported purification for a large number of elements after four completed passes in a static vacuum system operating at pressures less than 10-6 mm of Hg and with rates of zone travel between 30 and 40 mm per hr. He did not report oxygen concentrations, but stated that there was inverse segregation of this element. westlake5 has also used a minimum of four zone passes to remove iron from zirconium. No rates or conditions were given. Belk6 has shown that tungsten contamination can occur during electron-beam melting. He reported an increase from 0.01 to 0.05 pct by weight tungsten in molybdenum after four complete zone passes. The vacuum system for the electron-beam unit used in the present investigation consisted of a single-stage rotary pump backing a liquid-air-trapped oil-diffusion pump. A pressure of less than 10-8 mm of Hg was obtained with Dow-Corning 705 fluid in the diffusion pump. In order to avoid contamination of the zirconium by evaporation from the tungsten filament, a special focusing cage4 was employed. Three rates of zone travel, 114, 38, and 4 mm per hr, were investigated, with the liquid zone moving from the bottom to the top of the bar. The bars used were 3 mm diam and the total melted length was 130 mm. Oxygen was analyzed by neutron-activation analysis using a neutron flux of 10' neutrons per sq cm per sec to form the isotope N16 by the 016 (n,p) N16 reaction. The standard deviation is quoted for each oxygen determination. The iron and tungsten analyses were performed spectrographically, and the precision is estimated to be ±6 pct. Analyses for tungsten were all below the detectable limit of 10 ppm, confirming the protection given by the focusing cage. No significant redistribution of oxygen was found at the two higher rates of zone travel. The redistribution of oxygen and iron obtained after five passes at a rate of zone travel of 4 mm per hr (1.1 x 10-4 cm per sec) is recorded in Tables I and 11. Burris, Stockman, and Dillon3 have estimated the distribution of solutes during multipass zone refining. Using their curves for an effective distribution coefficient of Keff = 1.5 and 2 for oxygen and Keff = 0.3 for iron, the expected concentrations were estimated for the present material. These are shown in Tables I and 11, along with the experimentally measured values. The calculated concentrations are based on a molten-zone length of 10 pct of the total melted length, whereas in the present experiments the molten zone was approximately 5 pct of the total melted length. The effect of zone length on solute redistribution is most pronounced after a large number of zone passes. Comparison with Pfann's published data8 for solute redistribution for various Keff's and zone lengths indicates only small differences at low numbers of completed zone passes. It is evident that the expected distribution has not been realized in the case of iron. Scrapings of material deposited on the inner surfaces of the electron-focusing cage were found to be magnetic. It is, therefore, concluded that redistribution of iron is masked by evaporation. Deposition of iron inside the focusing cage was observed at all rates of zone travel. The results of the investigation may be summarized as follows: 1) Segregation of oxygen is typical for a solute with a distribution coefficient, Keff > 1. 2) No redistribution of oxygen takes place at high rates of zone travel. 3) The distribution coefficient for oxygen lies between 1.5 and 2.0. 4) Purification with respect to iron occurs mainly by evaporation. 5) The focusing cage is effective in preventing tungsten contamination.

Jan 1, 1967

By Richard J. Gonzalez

The petroleum industry includes varied and extensive operations required to supply increasing quantities of refined petroleum products and natural gas that are essential for the economic progress of an expanding population Petroleum has provided the power for the transformation from the "horse and buggy days" to the age of jets and space exploration, and for the remarkable improvement in productivity per worker in agriculture and manufacturing. Without increasing quantities of oil and gas, the world would face painful readjustments to more expensive forms of energy and lower standards of living Petroleum operations start with exploration, development, and production activities that supply the basic crude oil and natural gas Pipelines, ships, barges, and trucks first transport the raw materials to processing centers and then move the finished products to the ultimate consumers. Processing plants extract liquids from natural gas and refineries convert crude oil into a wide range of products These products include transportation fuels, feedstocks for conversion into numerous products (such as fabrics, rubber, and plastics), light fuels for heating, lubricants, and heavy residual materials (industrial fuel oil, asphalt, and coke) The final activity of wholesale distribution and retail marketing moves products into millions of homes, farms, industrial plants, and motor vehicles The use of coal exceeded that of oil and gas until 1946 in the United States and until 1968 in the rest of the world. However, oil and gas have proved to be such convenient and attractively priced fuels that they now supply three-fourths of the total commercial energy (including coal, hydroelectric, and nuclear power) used in North America and more than one-half in the rest of the world. LARGE SCALE OF OPERATIONS By the beginning of 1970, world crude oil production exceeded 43 million bbl daily, -equivalent to more than 2200 million tpy In addition, natural gas and the liquids recovered from processing natural gas supply about 40% as much energy as crude oil Production of oil and gas provide by far the highest value of all mining operations. In the United States, the value of oil and gas production in 1969 of $13 8 billion exceeded the $13 0 billion value for all other minerals The rate of expansion in use of petroleum has been extremely rapid since World War II World crude oil production doubled from 7,500,000 bbl daily in 1946 to more than 15,000,000 bbl daily by 1955 It doubled again to 30,000,000 by 1965, and will double again by 1975 The use of natural gas has increased greatly in the United States and also in Europe, as important discoveries in the Netherlands and the North Sea and technology for moving liquefied natural gas from Africa provided attractively priced supplies

Jan 1, 1976

By P. Barnes

It cannot be said that this whole subject is a new one in respect to its presentation to the Institute, but the minute discussion of it has been looked upon as lying more strictly within the field of study of the societies which have to do chiefly with the construction and management of machinery as such. It must be true that the importance of close limits in steam-economy is as fully recognized among the members of this Institute as by any body of men who have to do with steam-machinery. In all directions, nevertheless, among manufacturers as well as among metallurgists, there may still be found those who do not give the same attention to exact methods in fuel-consumption as devoted to steam, as to other technical uses which, to say the least, are not more important. The study of the most efficient methods of use of fuel in operations which are more strictly metallurgical has been long-continued, and in some directions nearly or quite exhaustive. This has led to a rather close bringing-up, in those particulars, all along the line of technical work, of the establishments (and their managers) which had lagged behind. Yet, in the steam-departments of those works, there are too many reasons for believing that the name may still be legion of those whose methods and results are far from the best. If there be room in any given case to suspect any imperfect working or waste of fuel in the steam-supply, the search for the evil, the clear fixing of its cause, and the application of the remedy are, or certainly ought to be, too obvious in their pressure for attention upon a manager to call for even so scanty a mention of them as can be accorded in this paper. It is natural that men should be incredulous as to imperfections which may be noted as existing in their machinery or methods. Still more are they likely to be altogether disinclined to admit that there may be thus an actual and palpable leakage in the compartment of their money-drawer devoted to coalsupplies. But the laws which govern the combustion of fuel, the

Jan 1, 1885

By R. A. Greenkorn

This project originated in a practical problem—we needed five tracers that could be used together to locate flow paths in a pilot flood. While tracers for subsurface liquids have been used since the turn of the century,1-15 none of those reported in the literature appeared to be either consistent or quantitative enough for our purposes. Most were used in field systems without controlled experiments to determine the accuracy and precision of analysis, and many were tracers that could not be used collectively. The ideal tracer, of course, would follow the fiuid of interest exactly, traveling at the same velocity as the fluid front. But the ideal is impractical to attain because adsorption-desorption effects cause the tracer to lag behind the front; these effects, plus diffusion-dispersion effects, cause the tracer front to spread more than the fluid front. Thus, our objective was not to locate a tracer that would be ideal for all circumstances but rather, to find one that would approximately follow the fluid, or one that under controlled conditions could be corrected to calculate the movement of the fluid front. We considered tracers satisfactory—(1) if they were easy to analyze; (2) if their breakthrough-elution curves were not too different from those for the chloride ion, a tracer believed to follow the fluid front closely; and (3) if we could calculate from the curves a material balance, at 1.25-PV (pore volume) injected, within 5 per cent of that calculated from chloride curves. Of a possible 35 materials, we selected 13 tracers that could be quickly and easily identified and whose analysis was claimed to be accurate within 5 per cent. Only one of these, tritiated water, was a radioactive tracer. Radioactive tracers are easy to detect even in small quantities, but they require special handling and special equipment. Also, those that can be used together are limited because special equipment is required to separate emissions from the various tracers. Two of the original 13 tracers were eliminated in static tests to determine how accurately and precisely they could be analyzed, and to check on gross adsorption. The remaining 11 were flowed through a 9-ft linear sandstone model, and breakthrough-elution curves were obtained. Finally, three tracers were field-tested as breakthrough tracers. These tests are described in the following sections. The 13 tracers considered in these experiments were EDTA (ethylene diamine tetra acetic acid), fluo-rescein, picric acid, salicylic acid and ammonium, boron (as borate), bromide, dichromate, iodide, nitrate and thiocyanate ions, plus chloride ion and tritiated water. All but the chloride ion and tritiated water were subjected to static sand tests to eliminate the tracers that could not be analyzed quickly and accurately and to eliminate those that showed excessive adsorption. All but two of the tracers, EDTA and salicylic acid, qualified for flow tests on this basis. The procedures used in the static tests (see Appendix A for analytical details) were as follows. Each tracer (in the amount shown in Table 1) was dissolved in 1,000 ml of water. Then, 800 ml of this solution was added to 500 gm of sand, and the remaining 200 ml was reserved as a control standard. The sand-tracer mixture was agitated once a day over a 10-week period, and during this period we analyzed five duplicate samples from this mixture, along with five duplicate samples from the control solution. From the control-sample analyses, we constructed a control chart on which the sand-tracer analysis results were plotted. The control chart, and its use to determine accuracy and precision of analytical results, as well as the amount of adsorption, is described in Appendix B. The results of the static tests are summarized in Table 1, which lists the concentration c (concentration at time t) divided by c, (initial concentration). If there was no adsorption, c/c, = 1. The acceptable deviation from this value varied from tracer to tracer, depending upon the limits of analytical precision established for the different tracers. The best results were obtained with boron, bromide and dichromate, with all values falling within limits of accuracy and precision. Ammonium, iodide, nitrate and picric acid also were satisfactory, although the ammonium results were erratic. Flourescein and thiocyanate were unsatisfactory ini-

By H. B. Heller, T. J. LaChapelle

Phosphorus nitride has been used as a diffusant for introducing phosphorus into silicon under various conditions. It has a temperature -dependent rate of decomposition beginning in the 500°C range, increasing very rapidly above 1000 C, producing gas -eous phosphorus and nitrogen. Best control was obtained with a two-temperature arrangement, with silicon at the proper higher diffusion temperature. It is an easier compound to use than the usual P2O5 because it is nonhygroscopic and yields temperature-controlled surface concentrations together with excellent final surfaces. Surface doping nearly as high as that produced by phosphorus pentoxide has been observed for sources at 850" to 900°C. Reproducible high sheet resistances were obtained by using slow flow rates (1 linear in. per min) and staggered-baffle gas mixing with the nitride at 550°C. Both inert gas (argon, nitrogen) and oxidizing ambients have been examined. Oxygen reacts to produce anhydrous P2O5, consuming the source at a rapid rate. Nitrogen, except for short diffusion times, suppressed the dissociation reaction and sometimes produced inferior surfaces. Argon appears to be a more useful ambient. PHOSPHORUS is a common impurity atom which may be introduced into a semiconductor lattice to create a p-n junction or an nn contact region. Various investigators1-4 have described techniques which can be used with either elemental phosphorus or certain of its compounds. This paper discusses a newly available compound of phosphorus, phos- some processes silicon wafers are precoated with a phosphate glass which acts as the doping source. Although a nonoxidizing form like elemental phosphorus or a phosphine can be used, most diffusion methods usually involve the use of phosphorus pentoxide. Because of the rapid volatility of this compound, a two-step process is often used, combining a gaseous deposition to introduce a predetermined quantity of phosphorus into the silicon with a later redistribution to obtain the desired distribution and surface concentration. Such a process usually involves predepositing phosphorus at surface concentrations greater than 1020 cm-'. At such doping levels the phosphorus-diffusion coefficient appears to be strongly concentration-dependent.596 Distribution profiles5'9 for these high concentrations of phosphorus do not follow Fick's laws, having extended subsurface regions which appear electrically to be nearly uniformly doped with ionized impurity atoms. Radioactive-tracer experiments also show near-surface anomalies in the distribution profile. Additionally, it has been shown1' that the introduction of very high surface concentrations of impurity atoms into silicon (a step necessitated by the subsequent lowering of concentration during the redistribution) creates dislocations, even in material having no dislocations originally. For device fabrication the use of oxide masking introduces certain difficulties and limitations.7'8 The standard practice of using phosphorus pentoxide as an impurity source adds other problems to these because of the speed and ease with which this compound reacts with moisture present in any gas in contact with it. In fact, P2O5 is one of the fastest and most effective drying agents for gases. Because it is such an excellent desiccant, completely anhydrous phosphorus pentoxide is difficult to obtain and is even more difficult to keep dry. Adequately dry gloved boxes must be used for storage and transfer of the chemical. The presence of even traces of moisture will cause formation of phosphoric acids which, during the high-temperature diffusion, results in polyphosphoric acids of variable composition. Such reaction by-products end up as gradually accumulating viscous fluids in the cooler parts of the diffusion furnace. The calculation of the final solute distribution for

Jan 1, 1964

By C. G. Dunn

With respect to theories of recrystalliza-tion in metals plastically deformed. it has been said that the present status of this subject is far from satisfactory.1 It may also be said that before any mechanism of recrystallization for metals and alloys can be set forth in a satisfactory manner, there must be made available considerable data on orientation changes that occur during the deformation and recrystallization processes. Although extensive data have been published on recrystallization in single crystals and in poly-crystalline specimens, more results of a type that can be classified according to simple orientation changes would be desirable in this complex field. It might even be said that before classifications are made according to types of orientation changes, it may be possible to classify a considerable amount of data into certain kinds of orientation states if groups of common or nearly common orientation occur. Methods for computing the probability of occurrence for various types of groups have been published2 and it has been pointed out in particular that it should be possible to analyze orientation data for high-order twin relationships between old and new grains even when agreement is not at all exact. In this connection, work on recrystallization in silicon ferrite reported in a paper concerned with complex groups of annealing twins3 indicated that some data were consistent with primary nucleation OCcurring according to a second-order or a third-order twin transformation. However, further work in this latter direction was definitely needed. It is, therefore, the purpose of the present paper to report data and analyses for primary nucleation in silicon ferrite following small deformations that have been carried Out at the Pittsfield Works' Laboratory of the General Electric Co. Analyses have been made with the aid of standard groups of twins that are reported elsewhere.4 PReparation oF Specimens and Experimental Procedure The material used in the present investigation was taken from the same heat of steel as that .used in a prior report.3 The finished strip in both cases was made by the Allegheny-Ludlum Steel Corporation according to methods that produce a high degree of preferred crystal orientation. Samples with large grains had the following composition: 3.45 per cent Si, 0.003 C, 0.008 P, 0.020 S, 0,075 Mn, 0.03I A1 and 0.072 Cu. Thickness of specimens was 0.012 inches. Plastic deformation was produced by cold-rolling the samples on a mill with 8-in. diameter rolls, the plane of the sample in each case coinciding with an XY plane (the plane of projection for the stereo-graphic plots) and the elongation occurring in the X direction. In general, elongations were held to about 3 or 4 per cent.

Jan 1, 1945

By Archer E., Wheeler

COPPER operations in the Congo mean the operations of the Union Miniere du Haut Katanga, because there are no other copper industries there. There is a mine at Bwana M'Kubwa, a little way to the South, in Rhodesia, which has been operated on a small scale, and-another farther south, the Falcon mine, but in quite a different section of the country. This Bwana M'Kubwa mine has recently been reorganized financially and the Minerals Separation interests have taken an extensive share in it, so that it may come into operation. The Union Miniere's operations are in Katanga, the most southeastern province of the Belgian Congo, and the company's concession is in the southeastern part of that province. The usual route for going into the country is by way of Cape Town, thence over the South African Railways through Kimberly and Mafe- king to Bulawayo, then by the Beira, Mashonland and Rhodesia Railways to the Rhodesia-Congo border, passing Victoria Falls on the way, and finally by the Belgian road, the Chemin de Fer du Katanga, to Elisa- bethville, the African headquarters of the company. From Cape Town to the border it is about 2150 mi. and from the border to Elisabethville about 158 mi., making a little over 2300 mi. from Cape Town, by rail.

Jan 1, 1924

By R. H. Jacoby, M. J. Rzasa

Experimental equilibrium vaporization ratios (K values) were obtained for nitrogen, methane, carbon dioxide, ethane and hydrogen sulfide in two natural gas-absorber oil mixtures and in two natural gas-Elk Basin crude oil mixtures. For each mixture of constant over-all composition, data were obtained at 100°, 150° and 200°F and at various pressures in the range 200 to 5,000 psia. Some effects of composition on the K values were obtained to serve as a guide in choosing K's for engineering calculations on other mixtures. The pressure cell used to obtain the data is a new type and is described here for the first time. INTRODUCTION The phase equilibria of complex hydrocarbon mixtures such as natural gases, crude oils and their mixtures have been studied previously for the purpose of finding equilibrium vaporization ratios for the hydrocarbon constitutents. In a few cases, such non-hydrocarbon.: as nitrogen, carbon dioxide, and hydrogen sulfide were included in the mixture. studied because they occur. in the fluids obtained from petroleum reservoirs. The increasing occurrerce. of these non-liydrocarbon.; antl their growing economic importance. make it necessary to account for them more accurately in engineering calculation.: than is now possible using the meager published data. The available data for non-hydrocarbons may he classified into two groups: namely, binary mixtures of a hydrocarbon and a non-hydrocarbon. and mixtures containing three or more components, only one of which is a non-hydrocarbon. Amon: the former. phase analyses are available for two nitrogen-HC mixtures, tve carbon dioxide-HC mixtures and three hydrogen sulfide-HC mixtures. Data for more complex mixtures are available as follows: Nitrogen-Methane-Pentane'; Nitrogen-Methane-Hexane,'; Nitrogen-Methane-Heptane'; Carbon dioxide-Natural Gas-Natural Gasorline": Carbon dioxide-Natural Gas-Crude Oil". These data have been used generally lor engineering calculations, often with little regard for their precise applicability because data for the non-hydrocarbons in the complex mixtures being dealt with were not available. The use of K values from binary data for calculation:; involving complex mixtures is open to criticism because such K's are not a function of composition and very often show large differences from the K's for the same components in a complex mixture. Thus the effects of composition must be evaluated when obtaining K's for components in complex mixtures. Poettmann and Katz " varied the carbon dioxide content of their mixture.; from about five to ten mol per cent and found substantially no effect on the K values due to this change. This was not surprising since one might expect that changing a minor com-ponent by * three mol per cent would have little effect. It is more important to find the composition change which have the largest effect on the K values. For example. varying the methane or heptanes — plus compositions over a wide rangr may have a large effect on the K'. of all components in the mixture. Interesting data to this effect were obtained by Eilerts and Smith." It was toward these problems that the experimental data presented here were directed. EQUIPMENT The pressure cell used to obtain the data i:. somewhat dif-ferent from those which have been described in the past. Photographs of the equipment are shown in Figs. 1 and 2. Fig. 1 Shows. the front panel: from a .rated position at the right the

Jan 1, 1952

By S. S. Shen, M. J. Pool, P. J. Spencer, J. R. Guadagno

VERY few thermodynamic data are available for rare-earth alloys, partly because of the difficulties of obtaining the metals in sufficiently pure form and also because of their comparative scarcity up to the present time. The rare earths form a very interesting series in the periodic table in view of the progressive filling of their 4f subvalence electron shell and would be expected to provide useful information with regard to alloying characteristics of transition elements. It has been found in recent calorimetric investigations that the heats of solution of a number of the rare-earth metals in liquid tin are highly exothermic.1-4 Exceptionally strong bonding between rare-earth and tin atoms is clearly indicated in the liquid solutions. Continued thermodynamic studies of the behavior of rare earths in solution could thus contribute a great deal to present theoretical knowledge of alloying behavior and would yield an insight into bonding of a strength hitherto unencountered in liquid alloys. The determination of the heats of solution of the pure components in liquid tin is an essential preliminary to calorimetric work of this nature. Heats of solution of praseodymium, neodymium, and samarium in liquid tin at 750" ' and the heats of mixing of Pr-Nd solid solutions' have already been determined in this laboratory. The present investigations with lanthanum continue the study of rare-earth elements. Details of the construction and operation of the liquid metal solution calorimeter used in this work have been published previously by Pool and Peluso and no further description will be given here. The lanthanum used in heat of solution determinations was supplied by Lunex who quoted the purity as 99.9 pct. Their detailed analysis of the material is given in Table I. Samples of 0.0003 to 0.0005 g-atom were used for each run and great care was taken to remove all surface oxide prior to weighing. The samples were stored at all other times in a beaker of oil to prevent their otherwise rapid oxidation. The compounds LaSn (Cudu, L1P type structure) and La&, (structure not classified) were prepared from the appropriate quantities of the two pure components by arc melting under a purified argon atmosphere and once again great precautions were taken to avoid any subsequent oxidation of the specimens. Although no structural examination of the compounds was made, the consistency of thermodynarnic measurements carried out on twenty or so individual samples of each indicates that the compounds were in fact homogeneous, single phase alloys. Samples of the compounds consisting of 0.0003 to 0.002 moles were used in the calorimetric measurements. A solvent bath consisting of approximately 80 g of 99.9 pct pure Sn was used for each series of runs and its heat capacity was determined at regular intervals throughout the experiments using pure tin or tungsten calibration samples. Measurements were made of the heat of solution of lanthanum in liquid tin at 725", 750C, and 775°K and at compositions up to 2.21, 4.76, and 5.25 at. pct La at the three temperatures respectively. In every case, the heat of solution of lanthanum remained constant at its limiting value, within experimental limits, up to the highest lanthanum concentration investigated. Since no change in was observed, it was concluded that the liquid/liquid + LaSn, phase boundary had not been

Jan 1, 1969

By S. G. Lasky

EVENTS during and since the war indicate that the nations of the world are trying to initiate an era of international co-operation. Definitions and objectives include social, economic, and human considerations no less than political considerations. The mineral resources of the world and the absolute and relative position of each nation enter into this situation. The possible use of armed might, the application of sanctions, the international flow of commerce, the ways in which this flow may encourage or hamper international well-being, and the influence of international and domestic well-being upon one another are all matters that must take mineral resources into account. If the United States is to act wisely and forthrightly in such matters we must be thoroughly informed as to our position with respect to mineral resources. What is the mineral position of the United States? A variety of widely conflicting opinions are held in authoritative and intelligent quarters: (1) For practical purposes our mineral resources are already exhausted.

Jan 1, 1946

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Jan 1, 1940

By E. E. Donath

Application of the coal hydrogenation process for the production of chemicals is described. It has been estimated that a plant to produce 31,090 bbl per day of chemicals and fuels would cost $326,- 000,000. These products would consist of 6.1 pct by weight tar acids, 50.8 pct aroma tics, 16.4 pct LPG, and 26.7 pct gasoline. THE coal hydrogenation process is well known as a means for the production of liquid fuels from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aro-matics and of tar acids and tar bases. The relative amounts of heavy and middle oil—boiling above and below, e.g., 325°C—can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.' Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydrogen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catchpot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1953

By E. E. Donath

Application of the coal hydrogenation process for the production of chemicals is described. It has been estimated that a plant to produce 31,090 bbl per day of chemicals and fuels would cost $326,- 000,000. These products would consist of 6.1 pct by weight tar acids, 50.8 pct aroma tics, 16.4 pct LPG, and 26.7 pct gasoline. THE coal hydrogenation process is well known as a means for the production of liquid fuels from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aro-matics and of tar acids and tar bases. The relative amounts of heavy and middle oil—boiling above and below, e.g., 325°C—can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.' Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydrogen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catchpot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1953

By Guy Borden, Michael J. Rzasa

Laboratory data on bubble point pressures and reservoir volume factors have been correlated as functions of solution gas-oil ratio, calculated gas gravity of the pentanes-and-lighter fraction of the entire fluid, differential residual oil gravity, and reservoir temperatures. INTRODUCTION Several correlations of crude oil properties have appeared in the literature. D. L. Katz4 in 1942 presented five methods of predicting oil shrinkage. these being of decreasing accuracy for decreasing amounts of information available. M. B. Standing- in 1947 published three correlations of laboratory flash vaporization data of California crudes. From values of GOR (gas-oil ratio), gas gravity, liquid gravity, and temperature, his correlations will predict bubble point pressure, formation volumes of bubble point liquids, and two-phase formation volumes. Curtis and Brinkley2 in 1949 presented several correlations. From the gas-oil ratio, an approximation of reservoir volume factor and barrels of condensate recoverable per barrel of reservoir space may be obtained; along with liquid gravity and reservoir temperature, the GOR will allow prediction of bubble point pressure. These last cor- relations seem to be more qualitative than quantitative. Generally, laboratory bottom hole sample tests furnish information on solution gas-oil ratios, residual oil gravities. bubble point pressures, viscosities of oils, liquid shrinkages, and occasionally gas gravities. Each of these data has its own applications and use in reservoir engineering calculations. The particular uses of correlated bottom hole sample data are found in (1 Providing a basis for obtaining estimates of formation crude properties in fields where bottom hole sampling is impractical or impossible. (2) Greatly reducing the time in obtaining the desired information. (3) Determining the applicability of the results from various bottom hole samples to particular field problems. (4) Avoiding, in many cases, the uncertainties of sampling by replacing it with an element over which greater control can be exercised. (5) Permitting use of preliminary field data in application of production procedures before a bottom hole sample can be obtained and analyzed in the laboratory. (6) Serving as a check on data which may appear out of line. (7) Estimating for a particular type crude the appropriate equilibrium constants by working backward from the bubble point pressure. (8) Estimating original or other past history properties of reservoirs that were not sampled in the past. PROCEDURE Application of the published correlations4,6 to Stanolind laboratory data indicated that the general scheme presented by Standing" could give dedrable results if changes were made in parameter positions and scales. The correlation curves were drawn with all the variables having consistent gradations except the temperature increments which were drawn in to best fit the data. The variables from available Stanolind laboratory data are defined below: (1) Gas-oil Ratio: Gas is liberated at reservoir temperature by differential vaporization (or rather by a series of flashes, approaching differential vaporization) and measured at atmospheric pressure and temperature, at which the compressibility factor is assumed to be unity. The oil is the residual liquid remaining after the pressure has been reduced to atmospheric. For the gas-oil ratio both volumes are corrected to standard conditions of 14.7 psia and 60°F. (2) Gas Gravity: It was decided to arbitrarily divide the hydrocarbons of the entire bottom hole sample into pentanes-and-lighter and hex-anes-and-heavier, and use a calculated gas gravity of the pentanes-and-lighter for a correlating variable. (Sample calculation is shown in Table 111.) (3) Liquid Gravity: This is the API gravity of the residual liquid from the differential vaporization. The gravity is measured at room temperature and corrected to 60°F.

Jan 1, 1950