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By W. J. Moore, E. M. Swiggard, H. Shenker

Beryllium is the most soluble of the double-acceptor impurities in germanium; the solubility is at least 1 x 10 19 atoms cm3. Photoconductive, optical, and electrical measurements were made on a set of Ge:Be samples grown without other intentionally added imp~ivities. The excited-states spectrum of beryllium in germanium was determined both in zero field and in magnetic fields up to 30 kc. It was found that the absorption 0-f lines in the vicinity of the G line increased markedly with increasing magnetic field. The ioniza-tion energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mez: using the excited-states spectrum. An infrared detector using a Ge:Be element was found to have a normalized detectivity D* (50 p, 1000 cps, 1 cps) of 9 X ldO cm-~ps"~-w-'. The Ge:Be sambles exhibited low-field breakdown and inibzirity band conduction effects at low temperatures. WHILE the properties of most dopants in germanium have been thoroughly investigated, the properties of beryllium in germanium have had relatively little attention. Much of the work that has been done' has been concerned with the properties of singly ionized beryllium in germanium. The purpose of the present work was to determine the photoconductive and electrical properties of beryllium-doped germanium (Ge:~e) with a small concentration of other electrically active impurities. Ge:Be is of special interest since beryllium is the most soluble of the known double-acceptor impurities in germanium. MATERIALS PREPARATION A set of &:Be crystals with beryllium concentrations between 5 x 1013 and 1x 10'' cmm3 and without other intentionally added impurities was grown in a hydrogen atmosphere by the horizontal zone-refining techniques described by Swiggard and Shenker.2 The segregation coefficient of beryllium in germanium was found to be about 0.07 and its maximum solubility was found to be greater than 1 x 10'' atoms cm-3 which is in agreement with previous results.' Most of the crystals were found to have a small net concentration of shallow acceptors; for example, a crystal having a beryllium concentration of 1.1 X 1016 cm-3 was found to have a net concentration of shallow acceptors of less than 1.5 X 1013 cm-3. Ingots designed to have a beryllium concentration of 1 x 1017 cm-3 or less exhibited a loss of electrically active beryllium. That is, the beryllium concentration was lower than expected and the decrease of the beryllium concentration along the length of the ingot was much larger than expected. It is hypothesized that this effect is due to the oxidation of the beryllium by the residual oxygen in the system. This effect is similar to but not as severe as the effect observed with boron in germani~m.3, 4 OPTICAL ABSORPTION SPECTRUM The excited-states spectrum of neutral beryllium atoms in germanium was studied by measuring the infrared optical absorption spectrum. A typical spectrum is shown in Fig. 1; the labeling of the absorption lines follows that of Fisher and Fan.* The spacings between the observed lines and the D line are nearly equal to the corresponding spacings for the other ac -ceptors in germanium.5-7 By the use of the theoretical result67' that the neutral impurity ionization energy is 2.53 mev larger than the energy of the D line, the ionization energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mev at 4.2"K. This method yields a more precise value of the impurity ionization energy than the usual Hall effect method.' The absorption spectrum of Ge:Be was also measured as a function of magnetic field using a magnetic field parallel to the incident radiation and using unpolarized radiation. A typical spectrum taken at 30 kG is shown in Fig. 2. An unexpected observation is that the absorption of the lines in the vicinity of the G line (there is a strong possibility that some of these lines may be associated with lines other than the G line) increases with magnetic field. RESISTIVITY AND HALL DATA Measurements of Hall voltage vs temperature were made on several of the samples. The thermal activa-

Jan 1, 1968

By K. E. Brown, A. R. Hagedorn

Continuous, two phase flow tests have been conducted during which four liquids of widely differing viscosities were produced by means of air-lift through 1%-in. tubing in a 1,500-ft. experimental well. The purpose of these tests was to determine the effect of liquid viscosity on two-phase flowing pressure gradients. The experimental test well was equipped with two gas-lift valves and four Maihak electronic pressure transmitters as well as instruments to accurately measure the liquid production, air injection rate, temperatures, and surface pressures. The tests were conducted for liquid flow rates ranging from 30 to 1,680 BID at gas-liquid ratios from 0 to 3,-270 scf/bbl. From these data, accurate pressure-depth traverses have been constructed for a wide range of test conditions. As a result of these tests, it is concluded that viscous effects are negligible for liquid viscosities less than 12 cp, but must be taken into account when the liquid viscosity is greater than this value. A correlation based on the method proposed by Poettmann and Carpenter and extended by Fan-cher and Brown has been developed for 1¼-in. tubing, which accounts for the effects of liquid viscosity where these effects are important. INTRODUCTION Numerous attempts have been made to determine the effect of viscosity in two-phase vertical flow. Previous attempts have all utilized laboratory experimeneal models of relatively short length. One of the initial investigators of viscous effects was Uren1 with later work being done by Moore et al.2,3 and more recently by Ros.4 However, the present investigation represents the fist attempt to study the influence of liquid viscosity on the pressure gradients occurring in two-phase vertical flow through a 1¼-in., 1,500 ft vertical tube. The approach of some authors has been to assume that all vertical two-phase flow occurs in a highly turbulent manner with the result that viscous effects are negligible. This has been a logical approach since most practical oil-well flow problems have liquid flow rates and gas-liquid ratios of such magnitudes that both phases will be in turbulent flow. It has also been noted, however, that in cases where this assumption has been made, serious discrepancies occur when the resulting correlation is applied to low production wells or wells producing very viscous crudes. Both conditions suggest that perhaps viscous effects may be the cause of these discrepancies. In the first case, the increased energy losses may be due to increased slippage between the gas and liquid phases as the liquid viscosity increases. This is contrary to what one might expect from Stokes law of friction,' but the same observations were made by ROS4 who attributed this behavior to the velocity distribution in the liquid as affected by the presence of the pipe wall. In the second case, the increased energy losses may be due to increased friction within the liquid itself as a result of the higher viscosities. The problem of determining the li- quid viscosity at which viscous effects becomes significant is a difficult one. Ros4 has indicated that liquid viscosity has no noticeable effect on the pressure gradient so long as it remains less than 6 cstk. Our tests have shown that viscous effects are practically negligible for liquid viscosities less than approximately 12 cp. Actually there is no single viscosity at which these effects become important. These effects are not only a function of the viscosities of the liquids and of the gas but are also a function of the velocities of the two phases. The velocities in turn are a function of the in situ gas-liquid ratio and liquid flow rate. Furthermore, the role of fluid viscosities in either slippage or friction losses will depend on the mechanism of flow of the gas and liquid, i.e., whether the flow is annular. as a mist, or as bubbles of gas through the liquid. These mechanisms are also a function of the in situ gas-liquid ratios and the flow rates. It would thus seem that the best one could hope for is to determine a transition region wherein the viscous effects may become significant for gas-liquid ratios and liquid production rates normally encountered in the field. The viscous effects might then be neglected for liquid viscosities less than those in the transition region but would have to be taken into account when higher viscosities are encountered. There are numerous instances where crude oils of high viscosity must be produced. The purpose of this study has been to evaluate the effects of liquid viscosities on twephase vertical flow by producing four liquids of widely differing viscosities through a 1 % -in. tube by means of air-lift. The approach used in this study was as follows:

Jan 1, 1965

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.' This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",' and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,' and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,' part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,' in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,' again in agreement with the idea that oxygen is transported,

Jan 1, 1963

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was ('Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970

By John E. Conley

THE slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5 3/4 million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. USE OF WASTE SLATES FOR MAKING AGGREGATES The lightweight-aggregate industry has been discussed elsewhere4.5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done' on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. REQUIREMENTS FOR RAW MATERIALS As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of any low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig. I illustrates the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By David Reger

LITTLE new oil was found in West Virginia, during 1923, but there were important discoveries of gas. Most of the large oil producers have contented themselves with pumping old wells or in drilling only enough new wells in defined territory to maintain a fairly constant production, the attitude being that no, profit is made in producing high-grade oil at a low price and that an eventual loss is sustained by draining the reserves of a limited commodity that, at some more favorable time, will be of much value. The representative of one large company said: "We have done nothing but pump old wells during 1923 and we have made no plans for 1924." Careful attention to producing wells has been the rule, there having been few abandonments; the belief is prevalent that small wells will eventually become profitable under more favorable marketing conditions. In natural gas, the opposite point of view prevails. Because of the vast capabilities of the state for producing gas, its output being ahead of all others, great systems of transportation and distribution into the markets of four adjoining states have been built and a demand has been created that no present, or apparently potential, production can satisfy. This demand has become so great that large distributing companies not only discourage new applications for service but advise old customers to install coal furnaces for auxiliary fuel; some have requested public-service commissions to grant higher 'rates against large industrial consumers than those allowed for domestic heating. The response to this known market has been a rapid increase in price, both at the well mouth and at the door of the ultimate consumer, and the industry has become so stable that the only uncertainty, or hazard, appears to be the question of the presence of gas in fair quantity in a given territory under consideration. Several oil companies have now forsaken their policy of selling gas, wells outright when drilled and ;have organized gas departments to drill for gas and to dispose of the daily output by meter to distributing corporations. With such companies and with other producers whose interest is chiefly gas, the year has been busy and profitable. Some new territory of apparently large value has been proved and deeper producing sands in old fields have been tapped.

Jan 3, 1924

By E. T. Knight, John D. Gill

Much has been written and said concerning the alleged wasteful and uneconomic use of natural gas and petroleum. Espccially condemned has been the use of natural gas for the production of carbon black and the use of heavy fuel oil under steam boilers.' The critics of these usages of gas and oil have sought to make effective their verbal attacks on the industry by the repetitive expression of the words "inferior" and "superior" uses2 of petroleum. Thus, to employ natural gas for residential heating was to use it in a superior way; to use it for the production of carbon black was to use it in a wasteful and uneconomic way. To use petroleum for the production of automotive fuel was to use it in a superior way; to employ it as a residential fuel and as the prime source of power in an industrial plant was to use it in an inferior and uneconomic way. No doubt the objections to such employment of gaseous and liquid natural hydrocarbons originated in the belief that natural gas and petroleum are limited, nonregenerative mineral resources, and that the functions they perform can be just as well performed by other natural resources like coal13 of which practically unlimited reserves are known. The generations that have dominated each of the last four decades have counted reserves4 of petroleum in terms of a few years supply. Meanwhile, domestic demand for motor fuel rose spectacularly from a few million barrels in 1900 to more than 500,000,000 bbl. last year.5 The more imaginative and vocal critics drew startling word pictures of the catastrophe of 25,000,000 motor vehicles made useless and of the great automotive manufacturing and allied industries brought to an untimely end, and millions of workers left hopelessly unemployed by what they called the deplorably rapid depletion of the petroleum reserve. Many of the critics have been sincere advocates of the conservation of natural resources; many others, and in recent years probably the majority, have espoused the doctrine of conservation to promote their own self-interest rather than that of the public. The latest advocate of severe restriction in the use of petroleum for the alleged purpose of conserving the petroleum resource proposes to achieve that end by a bill,6 now before

Jan 1, 1938

An Engineers' Symposium was held Wednesday evening, Mar. 26, in the auditorium of the Engineering Societies Building, 29 West. 39th St., under the general auspices of the Local Sections of the American Institute of Mining and Metallurgical Engineers, American Society. of Mechanical Engineers, and the Society of Automotive Engineers. It was participated in by members of the American Institute of Electrical Engineers, American Society of Civil Engineers, American Chemical Society, American Electrochemical Society, American Institute of Chemical Engineers, American Society of Heating and Ventilating Engineers, American. Society of Refrigerating Engineers, New York Electrical Society, Brooklyn Engineers' Club, Illuminating Engineering Society, Institute of Radio Engineers, Municipal Engineers of the City of New York, Society de Chemie. Industrielle, Society of Chemical Industry, and the Society of Naval Architects and Marine Engineers. In opening the meeting the chairman, Gano Dunn,* said: The program calls this an engineers' symposium, which means a putting, together of things, and these things tonight are ideas of fundamental relations to the engineering profession and the engineering societies. Not only engineers, but all men nowadays are examining their views in respect to their relation to what we call Society. My conception of Society is that there is no such thing in the concrete sense of the word. It is an abstraction, and just in proportion as it is a generalization and broader in scope than the particulars from which it is drawn, so is it emptier of content. That does not mean that it is not important, but it does mean that we should be careful and not be led astray into a zeal for doing things for Society that we would not do for our fellow engineers and our brothers. The man who is unwilling to do something for his brother or fellow engineer and yet urges that same thing for Society-is thoroughly inconsistent and, in my opinion, wrong.

Jan 5, 1919

By T. D. Tiemann

The extraction of iron oxide from several types of siliceous iron ore by digestion in sulfuric acid solutions was investigated in the temperature range from 80 to 258°F at concentrations from 10-60% H2SO4. Degree and rate of extraction were found to be critical with respect to both temperature and acid concentration, requiring temperatures in excess of 250° F and acid concentrations of 50% to effect 80-90% extraction of iron oxide in 60 min. Rate of extraction is directly related to surface area and apparently controlled by the rate of chemical reaction. The activation energy was found to be approximately 25,000 cal per g mol. Extraction characteristics of the several ores were found to be similar. The Department of Minerals and Metals Engineering at the University of Wisconsin conducts a continuing research program to develop processes for the utilization of low-grade iron ore deposits such as the nonmagnetic taconites of the Wisconsin Gogebic range. Methods under study include high-intensity magnetic and high-tension electrical concentration, flotation, direct reduction and chemical extraction. Concentration of a number of low-grade siliceous iron ores by the extraction of silica in sodium hydroxide solutions has been reported by the writer and others in the literature.1,2,3,4 Residual concentrates containing as much as 65% iron have been obtained from taconites containing less than 30%. Currently an alternative approach is under study, namely the dissolution of iron oxides from siliceous gangue by extraction in acid, with subsequent recovery of the iron from solution. Such a process for extracting iron oxide from the low-grade oclitic deposits of Alberta with hydrochloric acid was investigated and described by Gravenor, Govett and Rigg.5 The current investigation, which is entirely devoted to extraction with sulfuric acid, is the subject of this paper. In part, the objective of this research was to determine the possibility of leaching iron ores in situ with sulfuric acid. The investigation of a recovery method is left to later research. The ores investigated contained hematite (Fe2O3) as the principal iron-bearing mineral and minor amounts of goethite (Fe2O3 .H2O), magnetite (Fe3O4), and iron-bearing silicates. The gangue was essentially quartz occurring as single crystals and microcrystalline aggregates. Detailed description of the ores may be found in the literature.1,2,4,6 A comparison of the specific ores used in this investigation is shown in the partial analyses of Table I. EXPERIMENTAL METHODS All extractions were made at atmospheric pressure using beakers with a mechanical stirrer for those tests run below the boiling point, and Erlenmeyer flasks for those at the boiling point. A thermostatically controlled hot plate was used for heating, and this maintained the mean temperature within the solution to within ±3°F during extraction. The sample of ore for extraction was weighed to + 0.02 g. For tests below the boiling point, the sample was added to the beaker containing the sulfuric acid solution at the desired temperature. For the boiling-point tests, the sample was added to the Erlenmeyer flask followed by distilled water and the

Jan 1, 1968

By I. H. Pratt

The results of a study on the preparation of thin-film capacitor structures are discussed. The dietectric source material was quartz which was sputtered and deposited onto aluminum electrodes and counter-electroded to complete the metal-oxide-metal structures. This configuration was utilized to evaluate the dielectric, the device characteristics, and related process parameters. The effect of gas sputtering pressure, magnetic field strength, source-to-substrate distance, and power density on the rate of deposition is shown. Increased film thickness uniformity over a 3 by 3 in. area by optimum substrate positioning is indicated. Dielectric constant, dissipation factor, dielectric breakdown strength, insulation resistance, heat treatment, capacitance, and dissipation over the range 400 Hz to 5 MHz are reported. In the fabrication of silicon-integrated circuits, silicon dioxide has found use as a material suitable as a diffusion mask, for surface passivation of the silicon, and for protection of conductive films used for interconnections. Its use as a dielectric for thin-film capacitors in film hybrid circuits has been limited, to a degree, for lack of a compatible processing technique and because of its relatively low dielectric constant. With the recent advent of practical metal-oxide-semiconductor (MOS) field effect devices, the material is now being used to insulate the gate electrode from the conducting channel in the silicon. In this latter application, more stringent requirements have been imposed on .the oxide. A comprehensive resume of the use of silicon dioxide in integrated silicon device technology has been compiled including oxide film and bulk properties, method of oxide formations, and their applications.' A relatively new process to deposit SiO, and other dieIectrics is by rf sputtering, and the purpose of this paper is to describe the behavior of capacitors fabricated with a dielectric which has been sputtered from a quartz target and to indicate the relative effect of several of the process parameters on the film deposition. Work on rf sputtering of SiO2 and other dielectrics has been reported utilizing a triode type of sputtering system as described herein or a diode self-sustained glow discharge system. 2-8 SPUTTERING The process occurs during an electrical discharge in a gas plasma which provides the ions for acceleration to the target to produce the desired sputtering. The necessary plasma can be generated by a dc glow discharge through application of a high potential between two electrodes at approximately 2 to 10 x 10-2

Jan 1, 1969

By L. C. Raymond

Valuations in the mineral industry differ from those of other enterprises because mines and oil wells have a definite life so cannot be considered a perpetuity. This requires that in any mineral-property evaluation the recovery of invested capital is necessary during the life of the property. Capital write-offs for nonextractive industries are assumed to be continuously plowed back to sustain the operation and produce yields on the capital invested. The extractive or mineral industry, however, generally attempts to return to the investor both interest and principal during the life of a property. Normally this is done currently and the dividend includes both items. Where the mineral property possesses large reserves and the life factor approximates a perpetuity, the return on investment is generally comparable to that of industrial stocks. The valuation of a mineral property, at best, is based on educated estimates and judgment factors. This is particularly true as it relates to estimating selling prices over a long term or assessing the quality of management. Also, it is possible to make various assumptions as to rapidity of working out the deposit, varying time for start-up of operations, varying earning rates, so as to obtain different results with the same basic facts. Thus it is not surprising that two engineers, irrespective of their abilities, may not agree exactly even when given the same facts, but their results should be close enough to be used in establishing a fair value for trading purposes. The valuation is no better than the source of basic data and the soundness of judgment factors. Fundamentally the basic principles of mineral valuation are similar for base metals, sulfur, oil, or any other mineral. Each mineral, however, requires an engineer to have a knowledge of such factors as its occurrence, distribution, mining and processing methods, and marketing problems in order to gather and analyze all the facts and data that have a bearing on the earning potential of the property. Present Value of a Mineral Property In essence the present value of a mineral property is a sum of money in today's dollars that future income from the property are worth. It differs from the total anticipated earnings by the amount of the interest that the unrecouped investment could be expected to earn during the period of recoupment. Thus, if one could accurately estimate what a mineral property will earn during its life, after deducting all operating, administrative, capital, interest, and tax charges, the determination of present value would be a relatively simple mathematical calculation. Normally, where the expected life of the mineral property extends beyond 20 or 25 years, the discounted value of earnings beyond this period is relatively small. The petroleum industry generally discounts the annual cash flow of an operation rather than earnings since, for tax-saving purposes, earnings are kept

Jan 1, 1976

Economic Significance of High-grade Concentrates BY PAUL M TYLER AND CARLE R HAYWARD (Min & Met, Dec, 563 4000 words) Generally pyro¬mctallurgical methods yield a higher recovery but cost more per ton of ore treated Milling methods are inherently cheaper for the reason that they do not involve dissipa¬tion of heat energy in slag formation, ctc It is vaguely realized that the smelter man could do a better job if he were supplied with purer raw materials but hard¬headed mill men have been offered little inducement to do a really good job of cleaning concentrates To do this may involve some sacrifice in percentage yield and in mill capacity and unless there is a compensating saving in freight and smelter charges, it simply is not good business to go beyond a certain point in the way of making clean concentrate Opportunities exist for eliminating one or more steps in the expensive series of processes for recovering various metals, or at least reducing the volume of materials that has to be handled at the most costly steps The beneficiation of nonmetallic minerals likewise affords numerous examples of over-all economies obtainable through more refined methods of mechanical improvement All this leads to the conclusion that perfecting selective processes for isolating pure minerals (e g, galena) virtually free from other sulfides as well as gangue may be productive of industrial economies Conversely, cheapening smelting methods may invade the field of mechanical improvement of ores but, as Kiphng said, that is another story

Jan 1, 1937

By F. Selig, A. S. Odeh

A second-order approximation to the exact solution of the diffusivity equation corresponding to the pressure build-up of a well producing at a variable rate is derived. This approximation is applicable when the well's shut-in time is larger than the total time elapsed since the well was first produced. The resulting equations are compact in form and easy to use. Thus, the need for Horner's' theoretically precise but rather laborious solution to the above problem is eliminated. In addition, these equations apply where the use of Horner's widely known approximate method is questionable. From a practical point of view, the reported method is best suited for analysis of drill-stem tests and short production tests conducted on new wells. INTRODUCTION The utility of drill-stem and short production tests in reservoir studies has long been recognized by the reservoir engineer. If interpreted correctly they could lead to a wealth of information upon which may depend the success or failure of reservoirs' analyses. Initial reservoir pressure and the average flow capacity are two quantities that are normally sought from a drill-stem and/or a short production test analysis. Pressures are the most valuable and useful data in reservoir engineering. Directly or indirectly, they enter into all phases of reservoir engineering calculations. Therefore, their accurate determination is of utmost importance. The flow capacity kh of the reservoir is indicative of its commercial capability. In addition, it can indicate the presence of a darnaged zone around the wellbore and, thus, the necessity for remedial measures. Of the several methods used to analyze drill-stem and short production tests, Horner's' method is by and large the most common. It applies to an infinite reservoir and or a limited reservoir where the effect of production has not been felt by the boundary. Horner's method makes use of the so-called "point-source" solution of the diffusivity equation. The point-source solution is approximated by a logarithmic function and the superposition theorem is utilized to give the familiar pressure build-up equation where is the shut-in time, q is in reservoir barrels per day and the rest of the symbols conform with AIME nomenclature. Eq. 1 was derived for a well which produced at a constant rate q from time zero to time t and was then shut in. In actuality, such a constant rate of production does not normally obtain. Therefore, a correction must be applied to Eq. 1 to account for the varying rates of production. Horner suggested two methods. The first, which results in a theoretically accurate solution, is rather lengthy and laborious and, thus, it is not suited for routine analysis. The second which has been termed a "good working approximation" is the one used by the majority of the reservoir engineers. In the second method, Eq. 1 is modified by simply introducing a corrected time t, and writing where q is the last established production rate prior to shut-in, and t, is obtained by dividing the total cumulative production by the last established rate. Horner's original paper does not give any indication that this method of correction is based on any theoretical justification. In addition, there is a question as to what constitutes the last established rate. In case of a drill-stem test some engineers use the average rate obtained by dividing the total fluid produced by the total flow time, while others calculate the average rate by dividing the total fluid produced by the last flow-period time. Obviously, different results obtain for the different flow rates used. Because of this, a simple method to the varying-rate case was developed which is theoretically sound and which defines clearly the flow rate and its associated time to be used in the calculations. The final equation arrived at is where q* and t* are a modified rate and time, respectively, and can be easily calculated. In addition, it is shown theoretically that Horner's approximate method, if used for a variable-rate case, gives the correct pressure but would not be expected to give the correct flow capacity. MATHEMATICAL ANALYSIS The general equation governing the flow of slightly compressible fluid in porous media may be written as The elementary solution to Eq. 4, representing an instantaneous withdrawal of Q units volume of fluid at the origin at t = 0, is known as the instantaneous sink

By W. H. Morris

I have been requested to present a paper on the slag from the basic Bessemer process, as prepared for fertilizing. Since Professor W. B. Phillips presented at the Birmingham meeting, in May, 1888, an able paper* on this subject, as it had been developed up to that time, there is little for me to add. Perhaps later practice may be best expressed by the homely proverb, " The proof of the pudding is in the eating." As the Pottstown Iron Company is the only concern manufacturing basic Bessemer slag in this country, the writer's personal experience in the use of it may be interesting. Our slag averages: P2O5, 21.37; SiO2,, 5.10; MgO, 5.90; Al2O3, 4.01; MnO, 5.56 ; FeO, 12.00; Na2O and K2O, 0.80; CaO, 45.26; total, 100.00. This gives over 76 per cent. of phosphoric acid and lime. In using this material for several years past on my lawn and garden, I have found it better than anything else I have ever tried ; and I am sure that any of you who had seen my green grass last month (January), wherever the ground was bare from snow, as bright as in early fall, would be forced to acknowledge the advantages of this soil-enricher. The grass on my private lawn, and around the company's office, is green the whole winter; and we have raised very good sod, by the use of this phosphate, where, without it, we were unable to get the grass to grow either from seed or by repeatedly sodding. The same statement applies to garden-truck; when the soil was first broken up, a good crop of vegetables was easily raised. My own gardener has had several premiums from Philadelphia seedsmen (notably, last year, the first premium for sugarcorn raised in the first part of July, being the first sample sent them). Our method of applying this material is to grind the slag very finely, so that at least 60 per cent. of it will go through a 150-mesh screen (i.e., say, 22,500 meshes to the square inch), and 90 per cent. through a 100-mesh screen (i.e., 10,000 meshes to the square inch). This fine grinding seems to be the main condition of success.

Jan 1, 1893

Discussion of the paper of H. M. WARREN, A. S. BIESECEKER and E. J. POWELL, presented at the New York meeting, February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 181 to 193. R.. V. NORRIS, Wilkes-Barre, Pa.-For many years the power requirements of breakers designed in the Anthracite. Region have been based on calculations made from indicator diagrams taken during operation, with various sections of machinery idle; these, while giving reasonably accurate figures, gave no intimation of the peak loads which have been shown so clearly in the paper. The high-speed flywheel for breaker rolls is new and shows a remarkable saving in peak power required, besides eliminating the stalling of the rolls from overload. The figures given are so far in advance of anything previously published that they will undoubtedly be used as a basis for future breaker design. It is to be hoped that the authors will continue this investigation and extend their paper by a description of the motors found best suited for this work. WILLIAM KENT, Montclair, N. J.-I notice on p. 187 reference is made to one of the difficulties being the starting torque, and it is proposed to use roller or ball bearings in order to decrease the high starting torque. I suggest that. before the roller or ball bearings are put in, an investigation be made as to the amount of the starting torque, as shown by wattmeter measurements and as to what the starting torque ought to be, theoretically, according to the energy formula; that is, how much starting torque is required to accelerate the rotating mass in a given number of seconds up to full speed. Having secured this information it may be found the amount to be saved by roller bearings is not very great. If it appears that roller bearings will not greatly decrease the starting torque, the next thing to be done is to have a special design of motor in which there is a field that can be made very strong at the start, by the use of extra poles or other means, and the next thing that may be done is to increase the speed from 10,000 r.p.m. to 25,000, which can be done with wire-wound flywheels, especially if the wires are made of vanadium steel.

Jan 5, 1916

Your esteemed favors transmitting my discharge as your representative on the War Minerals Committee have come duly to hand and the kind words of commendation contained are greatly appreciated. Like other war committees, The War Minerals Committee's business in Washington was to meet an emergency as best it could, and as soon as the emergency had passed pressure of personal responsibilities immediately scattered the individual members. A detailed report of the Committee's work is therefore impossible. But before the matter is closed I feel it incumbent on me to ask you to report to the Directors and the Council, and through them to the members of the Institute and of the Society, the inestimable value to our Committee of the unstinted support given by both your officers and members. The instant response to all requests for funds was of the greatest assistance in getting started with office force, stationery, etc., and led later to a regular organization in the Bureau of Mines, working under a special appropriation, which is still doing good work as the War Minerals Investigation under Dr. Spurr. The voluntary work of the special sulphur and manganese committees formed by the War Minerals Committee was of great value to the Government. Copies of private reports supplied were of much assistance. But the great service of engineers and geologists as a whole was rendered in connection with the passage of the War Minerals Bill by Congress. Though every assistance possible was rendered by the Bureau of Mines and the Geological Survey, by the close of 1917 our Committee had about reached the limit of its usefulness in the way of stimulating the various Government executive committees, bureaus and departments to a realization of the country's need of preparation for domestic production of "war minerals" and had found that special Congressional action was imperative if the war was to continue for anything like the time then generally feared. This was necessary not only 'to insure a. supply of war minerals but to make possible the appointment of some able mining administrator of large experience in the mineral industry who, with ample authority, could sit in the councils of the Government and see to it that the ever increasing autocratic powers the war was developing were used toward the mining industry so as to foster rather than crush the latter in its effort to produce sufficient raw material for war and essential civil requirements.

Jan 7, 1919

By John E. Conley

The slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. Use of Waste Slates for Making Aggregates The lightweight-aggregate industry has been discussed elsewhere4,5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. Requirements for Raw Materials As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of ally low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig, I illustratcs the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By John E. Conley

The slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. Use of Waste Slates for Making Aggregates The lightweight-aggregate industry has been discussed elsewhere4,5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. Requirements for Raw Materials As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of ally low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig, I illustratcs the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By William Fraser

SINCE the operative word in the subject on which I have been asked to speak is "international," I need hardly emphasize before such an audience as this that it is one which calls for some discretion on my part at the present juncture of world affairs, since, in some respects, it may not be devoid of a controversial aspect. For though the war is over, it has left behind it a sorry state of health in the political and economic complex of the world we live in; and however different may be the impact of these factors on each of us, yet none of us can any longer hope to devise a system or policy to escape from much of its controversial heat, or evade the obligation of doing what we can to diminish it. I would like, therefore, to consider with you how one great form of world enterprise whose range is coextensive with material civilization itself-that is, the Petroleum Industry-can make and is competent to make, a contribution to international health; for it is now an agreed commonplace that oil is arterial in the world's system and we need no telling that a healthy body needs healthy blood. Before embarking on my subject, let me assure you that I have no need to be told that this country before all others-and for obvious reasons is the major sounding board of opinion in matters affecting most aspects of the petroleum industry-technical, economic, national and international (but, may I please add parenthetically, not to the exclusion of quite a

Jan 1, 1947

By A. H. Kline, E. B. Zimmer, Zay Jeffries

It is well known that many properties of a given metal vary with the size of grain or cell. For most industrial purposes, where high ultimate strength and high elastic limit are desired, the manufacturer tries to produce a fine-grained structure. For some purposes, for example in transformer iron, a coarse-grained structure is desirable. The terms fine-grained and coarse-grained are used only in a relative sense. For example, a fine-grained cast copper might have grains 100 times larger than coarse-grained high-speed steel. Similarly, a finegrained steel rail might have grains or cells 100 times larger than coarsegrained wire, which was made of steel from the same heat. In some metals, the change in grain size is more appreciable khan the changes in any of the properties determined by the tensile test. Furthermore, in metals which have been annealed or subjected to high temperatures, grain size may prove to be a better indication of the life of the metal in use than the tensile test. One of the authors was able to supplant the tensile test with grain-size determinations in the control of metal for a specific use, the latter determination being more indicative of the life of the metal part than the tensile test. A grain-size determination with a tensile stest is, of course, more valuable than either singly. At present there is a decided dearth of data on actual grain-size determinations in metals, and consequently a corresponding lack of ability to interpret the determinations after they are made. It would be desirable to have correlation made between grain size and properties of metals, comparing thousands of determinations. In this way, grain-size determinations might be interpreted in much the same manner that tensile tests are now. Several Methods of Measuring Grain Size One of the chief reasons why more grain-size measurements have not been made is the excessive work involved in making a determination.

Jan 1, 1916