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By A. W. Schlechten, W. J. Kroll

As this paper is written, the only method for the commercial production of lithium metal is by the fusion electrolysis of LiCl-KCl mixtures, as first proposed by Guntz.2 The details of the industrial process have not been made public but Osborg8 stated that an efficiency of more than go pct is obtained with a lithium metal recovery above 95 pct and that the metal is 99.5 pct pure. Pletenev9 gave a power consumption of 66 kw-hr per kilogram of lithium metal produced with a salt consumption of 9 kg of LiCl and 0.4 kg of KCI. Pletenev's figures indicate a somewhat lower recovery than that given by Osborg. In a recent report on German lithium plants, Motock7 gives figures that are also less favorable than those reported by Osborg. At the German plants the lithium recovery in electrolysis was only 83.4 pct, with a power consumption of too kw-hr per kilogram of lithium. The metal averaged only 97 pct pure, with sodium and potassium as the chief impurities. The presence of SO2, SO3, Si02, Ba, Ca, and appreciable amounts of Na and Fe2O3 were especially disturbing in the electrolysis, and it was necessary to run the cell for some time to eliminate most of these impurities and condition the bath. It may be noted here that most of these impurities do not interfere with a thermal reduction process. These facts show that the present method of producing lithium is fairly efficient and would suggest that other methods could not compete. However, fusion electrolysis has certain drawbacks, such as the necessity of supplying costly, low-voltage direct current and of collecting and processing the anodic chlorine if it is not to be wasted. An even greater disadvantage is that lithium chloride must be used for an electrolyte. It is one of the most expensive salts of lithium, since it cannot be produced in anhydrous form by precipitation from aqueous solution, as is done with LiF or Li2CO3. The reduction of lithium by a vacuum process similar to the ferrosilicon method for the production of magnesium would have certain advantages. Small units, such as Pidgeon retorts, would give flexibility of production to meet demand, and a small plant would require moderate capital outlay. There is a possibility of using idle Government-owned magnesium plants for such purposes. The raw materials needed for vacuum thermal reduction would not have to be extremely pure, especially with respect to the iron and calcium content. This paper describes a series of experiments to determine the effectiveness of various agents for the reduction of lithium compounds. The investigation is part of a program of vacuum metallurgy con-

Jan 1, 1947

By G. D. Van Arsdale

THE paper of Mr. Posnjak presents a laboratory confirmation of the well known facts that air ox-idation of pure solutions of ferrous sulfate is slow and difficult and that, like many other similar reactions, the speed, may be greatly accelerated by the presence of other substances, often in very small amounts, the effect of the presence of copper being determined ex-perimentally in this case. However, it should not be. overlooked that copper is always present in heap leach-ing solutions in amounts equal to or greater than those in the experiments described; therefore the paper may be considered as an explanation of present results rather than a possible improve-ment to be added to present practice. It is not practicable and it does not pay to precipitate copper by ce-mentation below a point about 5 lb. per 1000 gal., equivalent to about 0.0005 mol. Cu. per liter, compar-ing with the approxi-mately 0.0009 mol. per liter of curve 2 in the diagrams given of course, also, in the heaps local concentrations are usually very much higher than this, which is also true of the effluent li-quors, so that I feel that it is safe to say that copper is already present in amount sufficient to realize, as large an accelerating effect as is practicable. Too much im-provement or refinement cannot be expected in a method of this kind, due to commercial limitations. It should be remembered that chemically and physically there is no sharp dividing line between leaching in place, heap leaching, and the usual tank leaching practice, practi-cally the same reagents being used in all three. From the viewpoint of extractions, etc., it is not common sense to apply leaching in place to an orebody carrying enough copper to pay for mining; and the same is true of heap leaching, for an ore carrying enough to pay for the crushing, handling, etc., of ordinary leaching. That is to say, leaching in place should properly be consid-ered only for an ore too low-grade to pay for mining, and heap leaching for the next higher grade, still how-ever too low-grade to pay for crushing and other re-finements. There is no advantage in leaching without mining or in heap leaching except lower cost of in-stallation and handling; on the other hand there are very distinct disadvantages which are inherent and which should prohibit their use except where necessity requires. The object of metallurgy is to make money out of the handling of ore, and it is purely a question of money as to how far we can go in "improving" or

Jan 7, 1927

By J. Visman

A simplified method of assessing the characteristics of a cleaning unit, including washability curves, yield figures, ash error, separating gravities, and error curve. FOR more than 25 years evaluations of coal cleaning units have appeared in many publications, and during this time considerable progress has been made in developing the theory and techniques of calculating washery results. A variety of characteristics have been defined over the years, many receiving general recognition during the first post-war Coal Preparation Conference in Paris in 1950. Coal preparation has become a science, and the approach to preparation problems is being revolutionized. Formerly, for example, if a coal operator wanted to know the performance of a given cleaning unit for a particular grade of his run-of-mine, he either shipped a carload to the manufacturer for a test run or relied on a report of a test carried out on a coal similar to the one he intended to clean. In modern practice the expensive, time-consuming test work generally can be avoided if the washability curves of the coal in question and the error curve of the cleaner are known. Normally a guarantee can be given on the strength of this information. General acceptance of modern standards has thus reduced the need for pilot-scale models of existing types of coal cleaners. Needless to say, the method requires exhaustive and accurate information on the cleaning unit and on all the additional circumstances affecting its results, information that ultimately can be secured only from actual tests made in the laboratory or in the washery. It is not the purpose of the present discussion to compare the merits of various characteristics, but to describe the general method of calculation, including a method of obtaining data with a minimum of laboratory work. All data presented here were derived from tests made at the plant with portable field equipment, using small quantities of varsol, carbon tetrachloride, and bromoform. It will be explained later that the use of standard fractional ash contents designated normalized ash contents aids considerably in reducing the routine testing of coal cleaners. Like any other statistical procedure, this method has limitations, and it is not recommended for any work in connection with guarantees. Even a varying commodity such as coal, however, will follow the law of large numbers, which is the basic law of statistics, thus allowing simplification of test work without appreciable loss of accuracy. The characteristics needed for evaluating cleaner performance are normally derived from a float-sink analysis of samples of the clean coal and the refuse, followed by ash determinations of the various fractions. Usually a sample of feed is also collected to find its ash content and to make a single specific gravity cut, both in connection with determination

Jan 1, 1955

By J. K. Stanley

IT has been known for many years that the magnetic properties of a ferromagnetic material are very sensitive to internal strain. Any structure-sensitive property such as ferromagnetism, which is a-function of the regularity of the atomic arrangement, and discontinuities such as grain boundaries must show deviations from an equilibrium state when the regularity of the lattice is disturbed. Experience has shown that such distortions have a marked effect on the magnetic properties of a ferromagnetic material. The purpose of this paper is to show the feasibility of using magnetic methods in detecting internal strains. More specifically, it will be shown how such properties as permeability, remanence, and coercive force change on cold- working of aluminum iron and how these magnetic properties change during the annealing below the recrystallization temperatures. This work was conducted for two reasons. One was the desire to see in what manner strains are relieved in aluminum iron at low temperatures-a subject of practical importance in soft magnetic materials-and the other was the feeling that a study of cold-working and strain relief might shed some light honour understanding of what takes place in the deformation of metals DEFINITION IN TERMS It is necessary to define the terminology used in this paper because magnetic nomenclature is usually unfamiliar to the metallurgist, and certain other terms, such as recovery, have been used ambiguously by metallurgists and others. Magnetic terms are best explained by reference to the common hysteresis loop of ferromagnetic materials (Fig. I). In Fig. I the coordinates are magnetic induction, B, (ordinate) and magnetizing force, H, (abscissa). The c.g.s. unit for the magnetic induction is the gauss, the number of flux lines per square centimeter, and the unit for the magnetizing force is the oersted, the number of lines of force per centimeter in air or vacuum. If one starts with a completely de- magnetized specimen and magnetizes it, a typical virgin magnetization curve beginning at the origin is obtained. This curve is also the locus of tips of a family of smaller hysteresis loops. From this curve it is to be noted that the induction is not proportional to the magnetizing force, and that it appears to approach a limiting induction called the saturation value, and does so for values of H of 1000 oersteds. The ratio of the magnetic induction (gauss) to the magnetizing force (oersteds) is called permeability, p. Thus µ = B/H and if the magnetizing force H (oersteds) is specified as 10 or IOO oersteds, the permeability is written as µ10 or µ100. This is the accepted notation, and will be used in this paper. The values of permeability for H = 10 or 100 are chosen as indices for

Jan 1, 1945

By C. V. Millikan

Temperature measurement in wells is an old practice and geothermal gradients have been of interest to geologists for many years.le2 Their application to the operation of oil wells is a more recent practice. It has long been recognized that temperature anomalies occur in drilling and producing wells but thermometers that could obtain a satisfactory record of the anomalies were not available. The normal geothermal gradient is con-sidered as being about one degree Fahren-heit for each 60 ft. of depth.4 This "nor-mal " gradient varies in different areas, but whatever it may be in an area there is little variation from the surface to as deep as the : drill penetrates. The normal gradient is appreciably changed by gas expanding ; from the reservoir into the borehole or by the movement of fluid through a borehole : while drilling, producing, or circulating. It is the resulting anomalies and abnormal gradients from which conditions in wells can be interpreted. Some of the applications of such interpretations are locating the position of oil or gas sands, permeable strata in a reservoir zone, gas-oil contact, source of water, casing leaks, and the top of cement behind casing. Thermometers A thermometer for use in wells must be sensitive and have a low thermal lag. The sensitivity should permit recording 0.2OF. or less for differential temperatures although the actual temperature need not be more accurate than 1°F. The thermal lag should be as low as rugged construction will permit in order to allow surveys to be made in a minimum of time. Of the several kinds of thermometers, these requirements are most easily obtained with the vapor-pressure, expansion, and electric-resistance types. Thermometers for use in wells may be self-contained—that is, the complete instrument is lowered into the well and a record made of the temperature—or the thermal element only may be lowered into the well and the temperature recorded at the surface. The vapor-pressure and expansion types are more adaptable for a self-contained instrument while the electric-resistance thermometer is more suitable for surface recording of temperatures. The self-contained instrument can be run against high pressure on a single wire line with only one operator required. The instrument and its hoisting equipment is easily portable and can be mounted on a small car. The disadvantages are a somewhat greater thermal lag and the necessity of completing a run before any temperature or temperature anomaly is known. A surface-recording thermometer has the advantage of being somewhat more sensitive and of having a lower thermal lag. The Operator can see what anomalies are encountered and can immediately change the running conditions of the instrument or the well conditions in order to obtain the most

Jan 1, 1941

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 James E. Berryman

A method is presented for calculating the pressure depletion performance of a gas-condensate reservoir from the original reservoir fluid composition using the laboratory determined pressure-production history and retrograde liquid accumulation as guides. Equilibrium vaporization ratios for this calculation were modified from published data until the calculated dew point pressure and retrograde liquid accumulation agreed with the values observed in the laboratory. The calculated results are compared with the produced gas composition determined by low temperature analysis during constant volume laboratory experiments of pressure depletion behavior. This comparison shows that the calculation procedure is adequate for determination of gas phase composition. Data from field separation tests in low temperature separators are presented which verify the applicability of published equilibrium vaporization ratios for a wide range of separator conditions. INTRODUCTION A reliable prediction of the pressure depletion performance of a gas-condensate reservoir is necessary in determining reserves and evaluating field separation methods. The predicted performance is also used in planning future operations and studying the economics of projects for increasing liquid recovery. Because the flow of fluid in a volumetric gas-condensate reservoir is usually single phase flow, the pressure-depletion per-formake is primarily a function of the phase behavior of the reservoir fluid. The properties of a gas-condensate system of major importance are: (1) compressibility factor at reservoir temperature and pressure; (2) dew point pressure; (3) composition changes of the vapor phase with pressure depletion; (4) recovery of original in-place hydrocarbons at any pressure; and (5) retrograde condensate accumulation. These properties are most generally determined by a pressure depletion-type experiment on recombined separator gas and liquid samples in the laboratory. ldeally the pressure-depletion performance can be calculated from the composition of the original reservoir fluid if the reservoir temperature and initial pressure are known.1,2,3 It has been reported "... comparison of such computations with depletion-type ex-periments on recombined samples in the laboratory have yielded results that appeared to be entirely adequate.". The success of such calculations is determined by the equilibrium vaporization ratios chosen, especially those for the higher boiling point hydrocarbons. It is the purpose of this paper to present a method for computing the change in composition of the vapor phase during pressure depletion by production using laboratory determined properties of the system to guide the calculation and to illustrate the use of the method with data from the Cockfield "D" sand of Washington field, St. Landry Parish, La. Results of field tests and laboratory analysis are included. As a result of this reservoir fluid study, a cycling program has been evaluated, the fidd has been unitized, and the cycling started in July, 1956.

Jan 1, 1958

By John L. Lamont, Walter Crafts

THE principle formulated by Grossmann1 for calculating hardenability of steel by multiplying the ideal diameter of "pure" iron-carbon alloys by factors for grain size and alloying elements has been confirmed on many steels and has proved useful in designing substitute alloy steels. Grossmann found that the typical behavior of the multiplying factors was to increase directly in proportion to the amount of the alloy present in a steel. However, the multiplying factor for the effect of silicon on hardenability was found by Grossmann to increase to a lesser degree as the amount of silicon was increased. In view of the in¬creasing use of silicon in heat-treating steels, the effect of silicon on hardenability is becoming more important. Calculation of the hardenability of high-silicon steels made at the Union Carbide and Carbon Research Laboratories, Inc., indicated that the multiplying factor for silicon increased directly in proportion to the amount of silicon present. A more extended study of high-silicon steels covering fairly wide ranges of grain size, carbon, manganese, and aluminum has confirmed that up to 2 per cent silicon the multiplying factor is directly proportional to the silicon content. Manganese and aluminum factors have also been determined. The results of the study offer strong confirmation of the general validity of Grossmann's multiplying principle. TESTING PROCEDURE Steels on which the study of the effect of silicon on hardenability was based were made in high-frequency induction furnaces using Armco iron and standard alloying materials. The ingots were forged to bars, and sections were normalized prior to machining Jominy hardenability test specimens. The Jominy test was carried out under standard conditions.2 The depth of hardness penetration for determination of ideal diameter at "half hardness" was taken at the hardness level indicated in Fig. 20 in Grossmann's paper by the solid line for 50 per cent martensite in plain carbon steel. The depth of penetration of hardness on the Jominy specimen was converted to ideal diameter by the relation given in Fig. 28 of Grossmann's paper. Chemical analysis was determined on a sample taken adjacent to the Jominy specimen. Aluminum was determined as "acid-soluble aluminum" rather than as total aluminum, as it is probably more representative of the aluminum that is effective as an alloying agent. In addition to the elements nominally present in the steels, analyses were made for residual phosphorus, sulphur, nickel, copper, molybdenum and chromium on one heat of those made with the same materials during the same period. Actual grain size was determined by microscopic examination of small samples quenched in water after receiving the same thermal cycle as the Jominy hardenability specimens. Chemical analyses, heat-treatment, grain size, and hardenability are shown in Table I representing three ranges of composition.

Jan 1, 1943

By J. K. Stanley

It has been known for many years that the magnetic properties of a ferromagnetic material are very sensitive to internal strain. Any structure-sensitive property such as ferromagnetism, which is a function of the regularity of the atomic arrangement, and discontinuities such as grain boundaries must show deviations from an equilibrium state when the regularity of the lattice is disturbed. Experience has shown that such distortions have a marked effect on the magnetic properties of a ferromagnetic material. The purpose of this paper is to show the feasibility of using magnetic methods in detecting internal strains. More specifically, it will be shown how such properties as permeability, rema-nence, and coercive force change on cold-working of aluminum iron and how these magnetic properties change during the annealing below the recrystallization temperatures. This work was conducted for two reasons. One was the desire to see in what manner strains are relieved in aluminum iron at low temperatures—a subject of practical importance in soft magnetic materials—and the other was the feeling that a study of cold-working and strain relief might shed some light onour understandingof what takes place in the deformation of metals. Definition of Terms It is necessary to define the terminology used in this Paper because magnetic nomenclature is usually unfamiliar to the metallurgist, and certain other terms, such as recovery, have been used ambiguously by metallurgists and others. Magnetic terms are best explained by reference to the common hysteresis loop of ferromagnetic materials (Fig. I). In Fig. 1 the coordinates are magnetic induction, B, (ordinate) and magnetizing force, H. (abscissa). The c.g.s. unit for the magnetic induction is the gauss, the number of flux lines per square centimeter, and the unit for the magnetizing force is the oersted, the number of lines of force per centimeter in air or vacuum. If one starts with a completely demagnetized specimen and magnetizes it, a typical virgin magnetization curve beginning at the origin is obtained. This curve is also the locus of tips of a family of smaller hysteresis loops. From this curve it is to be noted that the induction is not proportional to the magnetizing force, and that it appears to approach a limiting induction called the saturation value, and does so for values of H of 1000 oersteds. The ratio of the magnetic induction (gauss) to the magnetizing force (oersteds) is called permeability, . Thus u= B/H and if the magnetizing force H (oersteds) is specified as ro or 100 oersteds, the permeability is written as or l00 This is the accepted notation, and will be used in this paper. The values of permeability for H = 10 or I00 are chosen as indices for 106

Jan 1, 1945

By J. E. Chappelear

We are concerned with the problem of calculating the forces produced by passing waves on a submerged object (in particular a drilling barge) located on the ocean floor. We employ the linearized theory of waves (the Airy1 theory), since solutions are generally more easily obtained in such a theory. It will be indicated how an approximate solution to the problem can be obtained for waves of finite height by use of a linear combination of Airy waves. We shall assume the submerged object has an infinite length, thus neglecting diffraction and making the problem two-dimensional. We find that there is not a considerable difference between our solution and the usual engineering solution. The force, as a function of time, is plotted in Figs. 4 and 5, together with the usual solution for easy comparison. So far, no experiments have been found to compare with the results. As will be shown, the calculations can be extended to waves of finite height (Stokes2-Struik3 waves) in an approximate fashion. This can be done by calculating the force produced by each Fourier component of the wave, separately, and omitting the coupling between the various harmonics produced by Bernoulli's theorem. The problem and its boundary conditions will be briefly stated. We seek a function, +, the velocity potential, which is harmonic, ?2?=0...........(1) and which satisfies the boundary conditions ??/?n =0 .......(2) (the normal derivative of + is zero) on the ocean floor and the sides of the barge, and s??/?y = ?..........(3) on the ocean surface, where s = g/w2........(4) The physical reasons for these choices and an interpretation of ? are given by Lamb.' As previously stated, we assume also that the problem is two-dimensional. We set up our coordinates such that x = 0 is the center of the barge and y = 0 is the ocean floor. The coordinates are shown in Fig. 1, together with the location of the barge on the bottom. Our solution may be decomposed into a function which is symmetric about x = 0,?e, and one which is antisymmetric, +,, ? = ? + ?o...........(5) Thus directly above the barge we have as boundary conditions that for x = 0, ?o = 0, ...........(6) and ??e/?x = 0........(7) Now, far from the barge, we have that (for x positive and assuming the waves are incident from the left) ?e ? Ae cosh ky cos k (x + a) , . . . (8) and ?e ? Ao cosh ky cos k (x + ß) . . . . (9) where + means ". .. approaches ... for x large." Let us put Ae, Ao, and k equal to one, and remember that, in accordance with the derivation of Eq. 3, a sinusoidal time factor is to be supplied. Then we may rewrite Eq. 8 for ?e, and we find that

Jan 1, 1958

By John A. Brown

Granules are used primarily as roofing material. From the earliest times, man has been faced with the basic problem of providing protection for himself, his family, and his property against the ravages of the weather. Basically, this problem is no different today than in the past, except that today the trend is to demand shelter which is also colorful and distinctive. There has been a gradual evolution from the thatched roof to the modem ranchstyle home. In his search for a more permanent and more attractive roof, the home owner has utilized many mineral materials. All granules, whether slate or colored granules, are referred to by the asphalt roofing industry as "Slate Granules." Early Roofing Materials The development of mineral roofing in the United States followed two trends: first, the slate industry, and second, the bituminous products. The early colonists were familiar with slab slate construction from Europe and it was natural for them to continue with this type of roofing. As early as 1780, the forerunners of the present bituminous products were finding favor. Those early products consisted of saturating burlap or similar material with crude tar or pitch. This type of roofing was soon improved by dusting a variety of materials on the surface of the roofing to prevent adhesion while in rolls. Such factors as fire resistance and protection from the actinic rays of the sun soon followed. This started the general pattern which is still followed today, that is, saturating felt materials and supplying a uniform grade of crushed mineral to the surface. In commercial and public buildings, metal roofs found early favor. The attractive green color of verdigris-coated copper became a symbol of churches and institutions of learning. Aluminum roofing has become economical for large structures and is finding limited popularity in rural areas. Tile, asbestos, and cement materials, being weather resistant, found early acclaim and are still popular. Today, by far the most widely used roofing materials in the United States are asphalt products. Two important characteristics-economy and weatherability-account for their popularity. Influence of Building Trends on Roofing The postwar building boom in 1947 had many attractive features for the American people. The ranch-style one story type of home seemed well suited for suburban developments which sprang up in such profusion. As the roof in modern home construction is one of the most conspicuous aspects of its architecture, the home owner could now express his tastes not only in paint and landscaping, but could also select an attractive and harmonious roof color. Variety of Minerals Used Many naturally occurring minerals are used today in the roofing industry. Most widely used (and most noticeable to the public) is the granulated mineral surfacing applied to asphalt products. Selected natural colored granules as well as artificially colored granules are

Jan 1, 1960

By M. I. Sherman, J. D. H. Strickland

PRELIMINARY experiments in these laboratories showed that whereas pyrite1 produced only sul-fate the action of aqueous chlorine solutions on most other sulfide ores resulted in the formation of a mixture of sulfate and elemental sulfur, the production of the latter being favored by a very dilute solution of oxidant. The reactions taking place were obviously complex and only a detailed kinetic study could be expected to clarify the position and enable a prediction to be made of conditions leading to the rapid formation of metal salt and the economically desirable elemental form of sulfur. Galena was chosen for the first investigation as it is of widespread occurrence and is representative of a simple cubic lattice sulfide containing the monosulfide unit, S2-. Experimental Procedure The apparatus and general technique used in this work have already been described.' Analyses for chlorine and sulfate were carried out by the same methods as those used for pyrite. The lead in 1 ml aliquots of solution was determined polarographi-cally, after destroying chlorine with hydrazine hy-drochloride and making solutions 0.5 molar with hydrochloric acid. A large sample of Kansas galena, assaying at better than 98 pet PbS, was crushed and wet sieved to give fractions of —10 + 14, —20 + 28, —28 + 35, and —48 + 65 Tyler screen. The particles were almost perfect cubes and the apparent surface Per gram was calculated assuming each particle a cube Of side equal to the mean mesh opening. A volume shape factor, calculated as for pyrite, was exactly unity. The main apparatus was unsuitable for direct visual examination of the ore particles during the reaction. For this purpose a small cell from a Spekker Absorptiometer optical flats 1 cm apart) was l by a greased microscope slide after filling with oxidant solution. One or two ore particles were placed in the cell and the solution was stirred by a glass covered speck of iron wire activated by an external rotating magnet. The surface of an ore particle was examined under a binocular microscope at between 10 and 40 magnifications. Results Experiments were made under a wide variety of conditions, the form of presentation of the data being illustrated by Fig. 1, where the concentrations of chlorine, sulfate, and sulfur are plotted against time. The fictitious concentration of solid sulfur is used for convenience and is the molarity of sulfur which would be recorded if the elementary sulfur formed during the reaction were dissolved in the liquid iii the reaction vessel. As some lead sulfate is occluded with the sulfur on the ore particles the amounts of sulfur and sulfate formed during a reaction cannot be calculated

Jan 1, 1958

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 H. Becke, D. Stolnitz, D. Flatley, W. Kern

Zinc difhsions in gallium arsenide having surface concentrations as low as 5 x 10'' atoms per cu cm have been attained. A multiple-difhsion sequence is employed during which zinc enters the gallium arsenide from a silicon dioxide film in a solid-to-solid diffusion step. The technique is illustrated for the case of a zinc surface concentration of -1 x 1017 atoms per cu cm and a junction depth of 1.2 p. Radiotracer measurements of -0.1-p layers of gallium arsenide are used to delineate the resulting profile. A diffusion coefficient for zinc in pyrolytically deposited silicon dioxide is reported. ZINC is frequently used as an acceptor impurity in gallium arsenide. As examples, p-n junctions are formed using zinc-diffused layers in solar cells, lasers, and varactor diodes. For these purposes surface concentrations of 10'' to over loz0 zinc atoms per cu cm are desired and readily obtained from a vapor source. Diffusion of zinc into gallium arsenide to yield surface concentrations of about 1017 atoms per cu cm, however, is more difficult. For instance, oldstein' reports that large changes in the vapor density of zinc produce only small changes in surface concentration. Such low surface concentrations are necessary in forming the diffused base of a gallium arsenide double-diffused n-p-n transistor in order to obtain an adequate emitter efficiency. An alternative approach to zinc diffusion which can provide reduction in surface concentration of several orders of magnitude is the introduction of the diffusant from a solid source. This can be conveniently accomplished by using oxide films of the type generally employed for selective diffusion masking. Such oxides also serve to prevent the dissociation of the gallium arsenide surface at the high temperatures of diffusion. DIFFUSION PROCEDURE Fig. 1 illustrates the diffusion sequence which is employed for obtaining zinc surface concentrations in the range from 5 x lom to 1 X 10" atoms per cu cm. The description of technique will be given for the instance of -1 x 1017, which is typically utilized in double-diffused gallium arsenide transistor investigations at this laboratory. Tin- or germanium-doped gallium arsenide wafers drawn from crystals grown by horizontal Bridgman or Czochralski techniques are used, with bulk concentrations ranging from 1 to 3 X 10" carrier atoms per cu cm. Each wafer is chemically polished on the (iii) arsenic face using a mixture of five parts concentrated sul-furic acid, one part water, and one part 30 pct hydrogen peroxide at room temperature, followed by rinsing in deionized and quartz-distilled water. Pyrolytic silicon dioxide was chosen as the oxide coating because of the high quality of the films obtainable, the ease of their preparation, and the excellent control over film thickness and uniformity.

Jan 1, 1964

By W. C. Ellis, M. E. Fine

In the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;' the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition2 which has a large effect on other properties. The thermal expansion data for the system have been reported only from room temperature to 100 C and for this temperature range a minimum in coefticient in the rcgion of 50 at. pct cobalt is well established.3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the tcrrelation. Experimental Procedure The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 5c pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 1/2 in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for I hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,? the differential expausion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outcr silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested On a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A nonoxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1949

By James K. Stanley

PREFERRED orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.1 In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurgical literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanical properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important in- formation, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational under- standing of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing 'stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required-it is only necessary punch or machine a disk of the sheet material and insert it into the testing device.

Jan 1, 1943

By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By William Hurst

This is a presentation of the diffusivity theory for the calculation of the water drive on an oil reservoir in which the history of reservoir pressure with time are the essential parameters for the determination of the rate and cumulative water encroachment into a field. The main body of the paper is essentially the application of the principles underlined here to actual field data. It consists of the work plots of the radial-flow case, and includes a discussion of an illustrated problem for which the water-drive calculations are treated in conjunction with the volumetric-balance equation. The appendix is a mathematical treatment of the linear, radial, and spherical cases of water influx into a reservoir. Introduction The evaluation of oil reserves and the prediction of pressure behavior with different rates of production are related to the volumetric balance of the fluids entering and leaving the space occupied by the oil and gas originally present in the formation; that is to say, important information can be gleaned from a volumetric study of the oil, gas, and water produced from a formation as it affects the extent of change in volume of oil zone, the gas cap, and the amount of water influx from the adjoining water sands. It is not the purpose of this paper to enter into a discussion of the equation of volumetric balance, in which such pertinent information as subsurface sampling and the measurement of reservoir pressures play a predominant part, as this has been discussed in detail by others.1,2 However, there is an inherent difficulty that has limited the general application of this equation to a study of oil reservoirs; that is, the insufficient knowledge of the analytics for expressing the water drive on a field as a function of reservoir pressure. This to a large degree has been overcome and it is the purpose of this paper to present this theory in such form as to be applicable for reservoir calculations. Water Drive If the amount of oil originally in place and the gas space are known, it is a relatively simple matter to determine, by the volumetric equation, the cumulative water influx into a reservoir from the adjoining water sands. Often, however, the oil reserve as well as water influx must be 'determined, and in order to be able to make this calculation it is essential to assign a mathematical relationship for the varying water term that is compatible with conditions known to exist in the formation and gives an accuracy acceptable for engineering calculations. Various equations have been employed empirically by different investigators in making reservoir studies of water drive. One form used by Schilthuis2 expresses the rate of water influx into a reservoir at any time as proportional to the pressure

Jan 1, 1943

By J. D. Rice, H. H. Rachford, G. H. Bruce, D. W. Peaceman

The problem of unsteady-state gas flow through porous media leads to a second-order non-linear partial differential equation for which no analytical solution has been found. In this paper a stable numerical procedure is developed for solving the equation for production of gas at constant rate from linear and radial systems. An electronic digital computer is used to perform the numerical integration using an implicit form of an approximating difference equation. Solutions are presented in graphical form for various values of dimension-less parameters. The solutions are compared with the laboratory study of gas depletion in a linear system. INTRODUCTION Production of fluids from porous rock reservoirs is essentially a transient process. Transient gradients develop as soon as production begins, and further withdrawals continue to cause disturbances which propagate throughout the reservoir, each adding in some way to the prior ones. A correct mathematical analysis of this behavior is complicated by the fact that the transient or unsteady-state flow of compressible fluids must be described by difficult second-order partial differential equations. As a practical matter, three distinctly different cases arise: 1. Flow of single-phase liquid 2. Flow of gases 3. Multiphase flow The first of these has been found to give a linear second-order equation similar to the well-known heat flow equation. where 7 is fluid density, 8 is time, and a a constant for the system, provided d 7 = r cdp, where the compressibility, c, is constant over the range of pressure, p, considered. Solutions of Equation (1) for both linear and radial flow are available in several forms.2'3' On the other hand. the second case, which is the flow of gas, gives a non-linear second-order equation, the solution of which is not known. Although a number of approximate solutions have been proposed, each is limited in value by the associated simplifying assumptions. Inasmuch as the analysis of transient flow is limited to liquid systems, a solution of the second case is necessary if further progress is to be made in studying underground fluid movement. For this reason a solution of Equation (2) was undertaken by means of numerical integration of approximating difference equations. BASIC DIFFERENTIAL EQUATION Equation (2; is derived by combining the equation of continuity, the perfect gas law, and Darcy's law to give the basic differential equation Strictly speaking, the fluids present in a gas reservoir are not perfect gases. Furthermore, there are indications that over certain velocity ranges, Darcy's law is not applicable. It would not be practicable. however, to attempt to obtain numerical solutions which would take into account all the possible variations from these laws which could occur in actual systems. The

Jan 1, 1953

By P. A. Beck, A. Merlini

Quantitative texture determinations were made for rolled and for rolled and annealed strips of 3, 6, and 10 pct Zn brasses. The main components of the rolling texture gradually shift over a wide composition range from the orientation characteristic of copper to that of 70-30 brass. At least the main features of the corresponding gradual changes in the annealing texture may be accounted for qualitatively on the basis of the oriented growth theory of annealing textures. All the oriented nucleation-type theories are notably less successful in accounting for the observed textures. EARLIER investigations by von Goeler and Sachs,' Dahl and Pawlek,' and Brick, Martin, and Angier" suggested that the annealing texture of copper is more sensitive to the addition of solute elements than the rolling texture. It was reported3 that the cube texture changes over into a brass-type recrys-tallization texture on addition of about 1 pct Zn, while the deformation texture changes only at about 5 pct Zn. Such behavior would be difficult to reconcile with any theory of annealing texture formation that relates the annealing texture to the deformation texture. In particular, the oriented growth theory of the cube texture" is based on a certain orientation relationship between the cube texture and the main components of the deformation texture which could not be reconciled with the reported behavior of low brasses. It was, therefore, of interest to re-examine these textures by means of the quantitative methods now available. The deformation and annealing textures of rolled a brasses with approximately 3, 6, and 10 pct Zn have been determined in terms of (111) and (200) pole figures. Experimental Methods The chemical analyses of the Cu-Zn alloys of commercial purity used in the present work are given in Table I. Chill-cast bars of the tabulated compositions were rolled and annealed according to the following schedule: I—rolling from 1.2 to 1.02 in. thickness, 15 pct reduction area, annealing 15 min at 450°C; 2— rolling from 1.02 to 0.867 in. thickness, 15 pct reduction area, annealing 15 min at 450°C; 3—rolling from 0.867 to 0.600 in. thickness, 31 pct reduction area, annealing 2 hr at 540°C; 4—rolling from 0.600 to 0.400 in. thickness, 33 pct reduction area, annealing 2 hr at 480°C. In the final straight rolling of 96.25 pct reduction area, the strips were reversed end to end after each pass. The final annealing temperature was determined for each alloy by annealing specimens of the cold-rolled strips in salt bath for 5 min at varying temperatures. The results of the hardness measurements are given in Fig. 1, where the final annealing temperature used for each alloy in determining the annealing texture is indicated by a cross.

Jan 1, 1956