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By H. C. Theuerer

EVEN the highest purity silicon available for semiconductor use contains significant amounts of donors and acceptors, usually aluminum, phosphorus, and boron. Aluminum and phosphorus can be removed from silicon by adaptations of the zone refining techniques' widely used with germanium. Removal of boron, however, has been a difficult problem. The approximate distribution coefficient for boron in silicon is 0.8, so that while zone refining is possible, it is not very effective in any reasonable number of passes. It has been found, however, that boron can be effectively removed from silicon by treatment of a liquid zone with hydrogen and water vapor. Starting with 40 ohm-cm, n-type silicon, use of zone refining coupled with hydrogen

Jan 1, 1957

By Morris Muskat

Analytical calculations have been carried out on the effect of casing perforations on the productivity of wells, and formulas have been derived for general types of perforation patterns. The numerical calculations, however, show that the resultant well productivity is essentially independent of the perforation pattern, but is determined mainly by the total perforation density. Thus, for example, for a density of three perforations per foot of casing, the well productivity will be cut to one third of that of the uncased well for a perforation radius of 1/8 in., and to approximately one half for a perforation radius of 1/4 in., regardless of the detailed manner in which the perforations are distributed over the casing surface. The analytical theory is also extended to include wells completed with slotted liners. It is shown that the reduction in productivity due to such liners will be relatively small as compared with that due to perforated casings. The increasingly important role being played by productivity factors of wells in determining well potentials and in the general evaluation of producing formations lends interest to the analysis of all the various factors that may infuence the productivity of a well. In recent papers1 the results have been given of theoretical studies made to determine the effect on the productivity factor of a well of the gas-oil ratio of the production and the connate water within the sand. These have served to show that both of these factors may, under suitable conditions, materially reduce the effective productivity factors below those that would be anticipated on the assumption that the wells produce homogeneous fluids. In this paper will be presented the results of the analysis of an entirely different factor influencing the productivity of a well. This refers to that resulting from the increased use of the method of completing wells by setting casing opposite all of the productive strata and then gun-perforating the particular zones of immediate interest. The practical success of this method of completion would appear to be an answer to the question as to whether it seriously reduces the well productivity or materially cuts down the ultimate oil recovery that may be derived from the producing section. Nevertheless, it is of interest to examine just how great the effect of the restricted flow channels, represented by the gun perforations, may be in increasing the over-all effective sand resistance. Of course, to the extent that the well potentials are severely restricted by proration regulations, minor reductions in well productivities are even less serious than if the wells were to be allowed to produce wide open. On the other hand, even under these circumstances there may be at least the academic interest in such calculations in being able to correct and evaluate the effect of the perforations in order to carry

Jan 1, 1943

By Morris Muskat

Analytical calculations have been carried out on the effect of casing perforations on the productivity of wells, and formulas have been derived for general types of perforation patterns. The numerical calculations, however, show that the resultant well productivity is essentially independent of the perforation pattern, but is determined mainly by the total perforation density. Thus, for example, for a density of three perforations per foot of casing, the well productivity will be cut to one third of that of the uncased well for a perforation radius of 1/8 in., and to approximately one half for a perforation radius of 1/4 in., regardless of the detailed manner in which the perforations are distributed over the casing surface. The analytical theory is also extended to include wells completed with slotted liners. It is shown that the reduction in productivity due to such liners will be relatively small as compared with that due to perforated casings. The increasingly important role being played by productivity factors of wells in determining well potentials and in the general evaluation of producing formations lends interest to the analysis of all the various factors that may infuence the productivity of a well. In recent papers1 the results have been given of theoretical studies made to determine the effect on the productivity factor of a well of the gas-oil ratio of the production and the connate water within the sand. These have served to show that both of these factors may, under suitable conditions, materially reduce the effective productivity factors below those that would be anticipated on the assumption that the wells produce homogeneous fluids. In this paper will be presented the results of the analysis of an entirely different factor influencing the productivity of a well. This refers to that resulting from the increased use of the method of completing wells by setting casing opposite all of the productive strata and then gun-perforating the particular zones of immediate interest. The practical success of this method of completion would appear to be an answer to the question as to whether it seriously reduces the well productivity or materially cuts down the ultimate oil recovery that may be derived from the producing section. Nevertheless, it is of interest to examine just how great the effect of the restricted flow channels, represented by the gun perforations, may be in increasing the over-all effective sand resistance. Of course, to the extent that the well potentials are severely restricted by proration regulations, minor reductions in well productivities are even less serious than if the wells were to be allowed to produce wide open. On the other hand, even under these circumstances there may be at least the academic interest in such calculations in being able to correct and evaluate the effect of the perforations in order to carry

Jan 1, 1943

By E. G. Woodruff

The earlier struggles in petroleum geology were directed to solving the Qrigin and method of accumulation of petroleum. We are now fairly well agreed on those subjects. Most of us think that the great mass of petroleum commercially produced comes from plants or animals, or possibly from both. We are confident that the oil was not produced where it is now found but has accumulated in reservoirs of various kinds. The types of reservoirs are certainly variable but they just .as certainly follow definite geologic laws. Some of these types of reservoirs can be determined from surface study; others cannot. We know, too, that these types of reservoirs (largely structures such as anticlines, domes, and terraces) are much more widespread than the oil pools. In other words, there are many places where good sands and good structures exist but where oil is not found. It is the purpose of this paper, therefore, to attempt to analyze, from a regional standpoint, some of the conditions that control the presence or absence of oil pools and to group them in a regional way, hence the term "Petroliferous Provinces." The paper lays no claim to presenting new facts but attempts to group and classify the information that so many have expressed again and again. The essential factors for an oil field are petroleum, a reservoir material, and conditions under which the petroleum can enter the reservoir but cannot escape except through the drill holes. The paper will first discuss the source of petroleum as it occurs in definite regions, then the regional arrangement of reservoir strata, and finally the areal arrangement of structures. To have petroleum, there must be a source. Since living matter is considered the source of the petroleum, geological conditions must have been such that living organisms were abundant. Arid regions on the earth's surface have not given rise to living things in sufficient abundance to produce oil; similarly, too cold regions and saline inland lakes. The converse of this is that warm moist conditions must prevail to produce an abundance of vegetable matter. Before an area can be

Jan 1, 1921

By A. J. Nicol

Field experience in uranium has shown it is most economical to ram through a drilling program to obtain maximum footage per drill hour. Drift surveys can then determine the course of the holes. Using this method is generally cheaper than paying the additional cost involved in using the drilling technique and equipment necessary to maintain straight holes. Factors Affecting Direction of Bit Travel: In all rotary-drilled holes there is an interplay of forces or conditions affecting the direction of bit travel. Rarely is a straight vertical hole obtained. One of the major factors is weight on a drill string. In looking at a joint of drill stem it is hard to imagine its being quite flexible, but flexing of the steel increases when many joints are made up together, and even a slight weight added to the upper portion causes a buckling or spiraling effect in the hole. The result is that the bit deviates from the vertical.

Jan 1, 1959

By J. E. Harris, J. A. Whiteman, A. G. Quarrell

The graphitizing reaction has been studied in a number of Fe-C-Si alloys in the temperature range 550° to 725°C. The TTT relationships exhibit "C" curve behavior except where nuclei, either foreign or graphite itself, are present before the start of the reaction. It is suggested that the rate -controlling process is diffusion of carbon through ferrite. For the reaction to proceed at the observed rate it is calculated that the matrix surrounding the particles must deform plastically; experimental evidence for this deformation is presented. It is well-established that the decomposition of austenite to pear lite occurs at a maximum rate at an intermediate temperature.l-5 This "C curve" be- havior, which has been reported in a number of other systems,5-10 is a consequence of the relatively low rate of nucleation of the pearlite at small degrees of undercooling of the austenite. The cemen-tite phase in the pearlite is, in turn, metastable with respect to graphite and if steels are held for prolonged periods at elevated temperatures decomposition of the pearlite occurs. It is difficult to predict the shape of the subcriti-cal graphitization TTT (time, temperature, transformation) diagram for, in this case, undercooling does not occur. However, the free-energy change for the reaction does decrease with increasing temperature" (Fig. 1) and it is thus anticipated that the rate of nucleation will fall as the temperature approaches that of the eutectoid. In addition, a decreasing growth rate with increasing temperature is predicted in some circumstances with pure Fe-C alloys. However, apparently similar conditions exist for first-stage graphitization in the austenite range (malleabilization) but no evidence for C curve behavior has been presented in the extensive liter-

Jan 1, 1965

By M. R. Tek, M. L. Katz

The flow of fluids in stratified porous systems, in which adjacent layers of the system are in communication over part or all of their common interface, in many instances involves crossflow between layers. A theoretical study has been made of the unsteady-state flow of slightly compressible fluids during depletion of bounded stratified porous systems. Consideration has been restricted to single-phase flow, with negligible capillary and gravity effects. Analytical expressions have been derived for pressure distribution and for (luxes at the producing face in two-layer systems with complete fluid communication between layers. These expressions occur in the form of double Fourier and Fourier-Bessel series. The method of extending the solution to any number of layers is demonstrated by deriving the equation for pressure distribution in a three-layer system. On the basis of the exact results for two-layer systems, certain generalizations regarding the behavior of stratified systems in general are presented. The performance of stratified systems, in terms of cumulative flux as a function of time, is shown to lie at all times between bounds established from single-layer theory. The upper bound is given by treating the system as a single layer with arithmetic average physical properties. The corresponding lower bound is the summation of the fluxes from each layer as treated individually. Variation in performance of stratified systems between the upper and lower bounds is determined by the extent to which crossflow occurs in the system. The principal parameters affecting the amount of crossflow are the vertical permeability of the system, the ratio of system thickness to "radius of drainage" and, for radial systems, the ratio of system thickness to interior radius. At very early times, the system performance is near the lower bound. As time and the radius of drainage increase, the per- formance tends toward the upper bound. INTRODUCTION One of the principal problems confronting the reservoir engineer today is the incorporation of the effect of reservoir heterogeneity into predictions of reservoir performance. The first part of this problem is the characterization of the actual reservoir heterogeneity in a mathematically useful manner.1, 2 It is then necessary to calculate the effect of this heterogeneity on the system performance. It is frequently possible to estimate this effect by comparison with the known behavior of an idealized system. One such idealized system is the stratified or "layer-cake" model. Many studies have been made of the behavior of stratified systems, from both a theoretical and experimental standpoint. The great majority of the theoretical studies have been concerned with systems of separated layers, with no fluid crossflow. Among the more noteworthy of such theoretical papers is that recently published by Lefkovits, et al,3 in which a comprehensive analysis was presented for the behavior of bounded stratified systems which are unconnected except at the wellbore. Three recent references have dealt with stratified systems including the effect of crossflow. Jacquard4 has presented mathematical derivations pertaining to depletion of two layer systems producing at constant rate. A doctoral dissertation by Katz5 contains analytical solutions and tables of results for pressure distribution and fluid flux during constant-terminal-pressure depletion of two-layer and three-layer systems with crossflow, together with tables of eigenvalues necessary in the computations. The dissertation also presents results from experimental studies of stratified systems using a heat-transfer analog model. This paper is largely based on the material in this dissertation. A third paper has been presented by Russell and Prats6 since completion of the work resented herein, containing mathematical derivations for and discussion of the behavior

The Institute is custodian of -funds for support of numerous gold medals and prizes and has representatives on boards awarding still others. Details regarding the Institute Awards are given below. The Institute is represented on the boards of the John Fritz Medal, the Hoover Medal and the Washington Award, in connection with the three national societies of Civil, Mechanical and Electrical engineering; and, also, in the case of the Washington Award, with the Western Society of Engineers. The Institute is represented with these four societies on the committee in charge of the Alfred Noble Prize.

Jan 1, 1938

By William Kent

A MOST startling and as yet unexplained, failure of steel boilerplates, in two different sets of boilers, is reported in a paper by Arthur J. Maginnis, published in the London Engineer, December 11th, 1885, and reprinted in the American Engineer, January 14th, 1386. The facts of the case, as condensed from Mr. Maginnis's paper and from a number of letters in the subsequent issues of the Engineer, are as follows: 1. The material used for two different sets of boilers on two different steamers, each set consisting of three circular boilers with horizontal steam-chests, passed all tests required by the Board of Trade

Jan 1, 1886

By William C. Overstreet, Paul K. Theobald, Jesse W. Whitlow

Monazite placers in a region of the Carolinas explored in 1951-1954 by the USGS are estimated to contain at least 53,000 short tons of thorium and 4600 short tons of uranium. None of these deposits is being mined. The 5200-sq mile area investigated extends northeast along the western Piedmont from the Savannah River in South Carolina to the Catawba River in North Carolina. Much of the region is 700 to 1100 ft above sea level. Gentle hills and broad interfluves give a local relief of 100 to 200 ft. This increases to 1700 ft at the west margin of the area where the east flank of the Blue Ridge is approached in South Carolina and the South Mts. are entered in North Carolina.

Jan 7, 1959

By W. M. Mobley

THE coal industry in Alabama, centered in Birmingham, has pioneered coal-beneficiation practice in the United States. The nature of the coal seams and mining methods employed have necessitated use of equipment and methods best adapted to the local conditions. Although all of the 30 or more coal seams now being mined in the state receive beneficiation, only the three most important producers of coking coals, the Pratt, Mary Lee and Black Creek, are discussed in detail. Nature of the seams, washability characteristics and equipment used are given as examples of the extent of work and progress in this field. The coal seams in Alabama are relatively thin and pitching, making mining difficult and expensive. Most of them are characterized by thin partings of rock or shale in the seam itself, as well as laminations of bone and rash. Mechanical mining methods have increased the occlusions from roof and floor to such an extent that nearly all the coal mined in the state must receive some treatment before it can be put on the market. During the year ending Sept. 30, 1943,1 18,129,792 tons of coal were mined in the state and 14,364,177 tons, or 79.2 per cent, received treatment. Excluding from the total the 1,223,014 tons produced by small wagon mines and the hand-picked lump coal, the amount receiving beneficiation would be more than 90.00 per cent. This is, by far, greater than in any other coal-producing state. The earliest record of coal beneficiation in Alabama was the installation in 1890 of an experimental Lung washer by Alexander Cunningham, for the Sloss Iron and Steel Co. at its blast furnace in Birmingham .2 In 1894 the Jeffrey Manufacturing Co. introduced the English Robinson washer, a combination of a hydraulic classifier and centrifugal machine. Erskine Ramsay, who has contributed so much to the coal industry, saw its possibilities as well as its mechanical defects and soon had his inventive mind at work. He added a sludge tank of his own design, and many Robinson-Ramsay washers were installed in Alabama and other states. The Stewart jig appeared in 1900, followed by the Montgomery jig in 1910 and both have found extensive use. Increased interest in this field led to new designs, such as the American, Elmore; Burke and Faust. The first Baum-type Norton jig was operated in 1930 and within the last five years six large installations of this type have been made by the McNally-Pittsburg, Jeffrey and Link-Belt Companies. Wet-washing tables were introduced in 1922 but not extensively used until recently. The two most popular types are the Deister-Overstrom and Deister Plat-O. The coal-cleaning equipment used in Alabama has been relatively simple, yet efficient, but as the amount of impurities in the raw coal has been increased by mechanical mining and labor costs have become higher, much interest has been shown in sand cones, froth flotation and

Jan 1, 1945

By A. A. Smith, J. S. Smart

THE controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modem copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range 0 to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously.1-2-3 Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,1, 2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of 3/8-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 850°C. from a surface scale. Test wires were drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at o.3125, 0.257, o.204 and o.162 in., and a final cold reduction of 95 per cent t0 0.081 in. Oxygen-bearing slugs made by remelting were hot-rolled to 5/16 in., drawn to 0.162 in., annealed for 30 min. at 600°C. and cold-drawn 95 per cent to 0.081inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 5/16-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700° to 800°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals were of one hour duration followed by a rapid quench in 10 per cent H2SO4. EFFECT OF PHOSPHORUS The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1945

By Clarence E. Sims, Donald W. Williams, George A. Moore

INTRODUCTION DURING the past several years the steel casting industry has made studies of heavy castings in which the test bar has been taken from heavy sections rather than from attached or separately cast coupons. It has been noted that the ductility properties of these heavy sections are often lower than those normally expected. Such lowered ductility is usually accompanied by a spotty test bar fracture and the ductility values often can be greatly improved if a low-temperature aging treatment is given to the casting. A loss of ductility of this type is considered "abnormal," since it is not accompanied by an increase of tensile strength or hardness, and "temporary" when the ductility can be restored by aging. The cure of such an abnormal condition represents a real improvement in the quality of the steel. Some hundreds of previous investigations, largely qualitative in nature, have established beyond reasonable doubt that hydrogen is normally present in newly manufactured steel and that this gas, in small amounts, can cause a temporary abnormal loss of ductility. The commonly observed association of high gas content and low ductility has given strong evidence for the presumption that hydrogen, possibly assisted by other gases, is the primary cause of the low ductility observed. Accordingly, the Steel Founders' Society of America has, since Nov. 1, 1944, sponsored investigations at Battelle Memorial Institute whose primary objective is to obtain quantitative information on the relation of the amount of hydrogen and nitrogen in steel, together with associated methods of steelmaking and treatment, to low-ductility effects and porosity. In order that these investigations might proceed on a quantitative basis, hydrogen analyses of a precision considerably higher than any previously reported in the literature were necessary. The method chosen was selected entirely on the basis that it had the highest probability of freedom from uncontrollable errors and will be described in detail in another publication.1 Briefly, the method used consisted of the hot extraction of solid pieces of steel weighing from 45 to 50 g in a highly evacuated quartz tube maintained at 1050°C (1925°F) for a period 0f approximately 40 hr. The greatest precautions were taken to eliminate blanks and insure a sound gas-collection system. Vacuum and temperature conditions were maintained automatically. Mercury-filled risers were used for the introduction of samples in order that the system could be degassed thoroughly in

Jan 1, 1948

By A. M. Hall

SULPHUR, even in small amounts, may often be harmful to nickel and high-nickel alloys, causing impairment of mechanical strength and destruction of malleability and ductility, as shown by Merica and Waltenberg.1,2 It may act. either in the form of nonmetallic inclusions produced in the liquid state during furnacing or as reaction products resulting from its diffusion into the solid metal. In recognizing the action of this element, ability to identify its various forms by means of the microscope is often of considerable importance, especially when direct quantitative methods are inapplicable. [ ] Of the sulphur compounds associated with nickel and high-nickel alloys, the sulphides that may be found in malleable nickel, Monel? and Inconel? are an important group. These sulphides were investigated by metallographic methods in order to provide descriptive data by which to identify them. The nominal compositions of malleable nickel, Monet and Inconel are given in Table I. The term "sulphide" is employed here in a very general sense, to designate a substance in which sulphur and one or more metallic elements are combined. The term includes any combinations of compounds and solid solutions. METHOD OF INVESTIGATION Three groups of small laboratory melts were made, one group to represent each of the three types of alloy under investigation. Within each group, a number of ingots with a sufficient variety of chemical analyses were prepared so that the effect of each of the elements entering the complete commercial alloy could be isolated and observed. In most cases, to facilitate metallographic study by exaggerating the number and size of the resulting sulphides, somewhat greater amounts of the minor elements were added than are present in the commercial alloys. Likewise, considerably more sulphur was added than is normal, but not enough to complicate the system. Transverse sections were cut at a point one third of the distance from the butt to the head of each ingot, polished and examined with an inverted stage metallograph equipped with a combination polarizing-analyzing vertical illuminator. The light source was a tungsten-mercury vapor arc lamp.

Jan 1, 1943

By F. F. Frick, Frederick Laist

In a leaching process, having obtained the copper in solution, the choice of the precipitation method is influenced by the following factors: 1. Availability of precipitant. 2. Adaptability to the leaching process. 3. Final product desired. 4. Regeneration of leaching solutions. 5. Fouling of solutions. There are three general classes of precipitation methods: 1. The use of iron, scrap or sponge. 2. Electrolytic deposition. 3. The use of some gas or reagent by which the copper is obtained, usually in the form of an intermediate precipitate which requires further treatment. For example, the precipitation of, the copper as Cu2Cl2 from chloride solutions; with SO2 gas. The use of iron is adapted to almost any process. It has the great advantage of extreme simplicity, and the recovery of the copper and any values present in a highly concentrated, easily treatable form. The disadvantages are the cost in isolated places, the uncertainty of the scrap-iron market, and the fouling of the leaching solutions. The latter is a serious factor, when a reagent such as salt is used in them, which makes necessary their re-use. Where applicable, electrolytic deposition is very attractive. The copper is obtained in a form directly marketable, there is a regeneration of acid and no fouling of solutions. Unfortunately, chloride solutions do not lend themselves to electrolysis. An entirely satisfactory anode material has not yet been discovered, although magnetite, apart from being rather brittle, seems to answer the requirements fairly well. The use of a method of the. third class is involved in many special

Jan 1, 1915

By Irwin Roman

IN studying the possibilities of a continuously recording magnetometer for use along the surface of the earth and in an airplane, the Federal Bureau of Mines was led to a study of the theoretical resolving power of magnetic observations, both in the variation of the total magnetic intensity and in each of the two components ordinarily measured. Along with this general study, an attempt was made to determine the relative worth of the total intensity anomaly and the vertical anomaly in geophysical prospecting. General considerations led to three conclusions: I. In the northern magnetic hemisphere of the earth, the total intensity anomaly is offset to the south of the vertical anomaly, for a positive anomaly (see Appendix, note I). 2. The resolving power of magnetic observations decreases rapidly with distance from the disturbing body. 3. The horizontal anomaly has little value in prediction of the disturbing body but might be useful in making a choice between bodies suggested by the vertical or total anomaly. Some of the considerations leading to these conclusions were: I. The normal intensity and the anomalous intensity are vectorially additive; hence for a positive anomaly in the northern magnetic hemisphere the total intensity will be a maximum at some point south of the disturbing body and north of the point at which the line to the disturbing body is parallel to the normal earth's field. The anomaly itself has a maximum value directly above the body. For a positive anomaly of constant magnitude, the total intensity will be a maximum when the anomaly vector is parallel to the normal vector. This is shown schematically in Fig. I (not to scale) for a magnetic distribution not restricted to a relatively thin sheet in the magnetic meridian. The normal field has a magnitude Io with vertical component Vo and horizontal component H,. Six station points along a traverse' across the body from south to north are shown at M to S. At each of these stations the normal magnetic field vector terminates at F. At each of these stations the magnetic field vector due to the disturbing body B terminates at A. The line through the station point and the point A passes through B. The magnitude of the anomaly, indicated by the length of the vector terminating at A, is proportional to some power of the distance from the station point to the disturbing body. If the' disturbing body B is a concentrated point of magnetic material, the anomaly is proportional to the inverse second power of the distance. For a uniform magnetic distribution over a line perpendicular to the observed traverse, the anomaly is proportional to the inverse first power of the distance. For surface distributions, the law of intensity is more complicated. At each field point, the total magnetic intensity T is the vector sum of the

Jan 1, 1946

By L. Larson

SMELTERMEN in the copper industry know that punching the tuyeres of a copper converter is a difficult, disagreeable, and at times a hazardous job. Knowing this, many men in the industry have given serious consideration to punching by mechanical means. As evidence of such consideration, a great many patents have been issued covering various mechanical devices or machines for doing this task. In 1942, as war-created manpower shortages became more acute, it became increasingly difficult to get men to punch tuyeres. Faced with this situation at the McGill smelter, it was decided that an all-out effort should be made to develop some sort of a mechanical punching device. The various patents were studied over thoroughly but none of the devices seemed suitable, all were discarded and it was decided to develop one, using the ideas of the personnel at McGill. Initial test work indicated that a separate punching device should be attached to each tuyere. This meant that an adapter would have to be developed which would accommodate such a device; the adapter to be so constructed that it could be substituted for the regular Dyblie valve head, and be punched either by mechanical means or by hand. Also a method for quickly attaching or detaching the punching unit would have to be devised. If the punching unit was attached to the adapter, then the punch rod and tip would have to remain inside of and reciprocate within the tuyere pipe. This last requirement meant that the punching device, the adapter, the piston rod, and punch rod must be in perfect alignment. The whole arrangement thus would become an integral part of the converter and would rotate along with the tuyere line to all the positions required for converter operation. If the puncher was to rotate with the converter, there was also a problem of limited clearance. The construction of a device to meet all of these conditions imposed many problems. In the latter part of 1942, two pieces of equipment were constructed and tried out under test-stand conditions. Both of these devices were very crude, but test-stand operation indicated that progress was being made. Neither of the units was considered good enough to be attached to and tried out on a tuyere of an operating converter. In May 1943, work was started on another device and in August of that year it was attached to and actually punched a single tuyere of a converter on an experimental basis (fig. 1). This unit was essentially a cylinder 3 in. in diam and about 15 in. long inside. Valve ports were so located as to provide a 1-in. cushion on each end of the stroke. The cylinder ports were piped to a 3/4-in. four-way disk valve. High pressure air (90 psi) was delivered to the valve by means of a long hose, thus making it possible to supply air to the device at all operating positions of the converter. The forward and return punching strokes were accomplished by shifting the valve handle as required. With the 3/4-in. valve, stroke velocities from 15 to 18 fps were achieved. Punching with this experimental arrangement was carried on for some time, but many difficulties were encountered. The punch rod tips often stuck in the tuyere accretion, indicating that more energy of some sort was necessary to avoid sticking the punch rod. To overcome sticking, experiments continued with a speeded up unit and although progress was made, troubles of various kinds continued to appear. On this unit, piston cup seals passed the valve ports which proved to be of very poor construction. Also the piston, driven forward at approximately 28 fps, would often bottom metal to metal in the forward end of the cylinder causing both mechanical and operational trouble. Sometimes the punch rod and at other times the piston rod would break loose and be shot through the tuyere pipe into the converter. Bottoming and poor timing of valve reversal caused a bounce and a hesitation at the end of the forward stroke, with the result that the punch rod

Jan 1, 1951

By Albert B. Horn, J. J. McKetta, O. L. Culberson

Since water is present in natural gas and petroleum reservoirs, it is of engineering value to have accurate experimental data regarding the behavior of water in hydro-carbon systems. Since experimental data of this nature are so scarce in literature, a program is under way at the University of Texas to obtain experimental data regarding the distribution of water in petroleum hydrocarbons. This initial paper is subdivided into three parts: A. The apparatus and analytical procedure are discussed. B. The equipment has been checked by comparing the experimental data with data of literature on the solubility of methane in water at 77°F and pressures to 10,000 psia. C. Experimental data are presented at 100, 160, 220, 280, and 340°F on the solubility of ethane in water at pressures to 1200 psia. As the temperature is increased the solubility of ethane in water first exhibits a minimum and then a maximum solubility. The range of applicability of Henry's Law is discussed. INTRODUCTION Although considerable experimental data have been published on water-hydrocarbon systems in the hydrate region, the information on these systems in the vapor-liquid and the vapor-liquid- 'References are given at end of paper. Manuscript received at the office of the Petroleum Branch August 31. 1949. liquid regions at elevated pressures is extremely scarce. A survey of the literature on hydrocarbon-water systems at elevated pressures was presented by McKetta and Katz12,13,14 showing the systems and phases investigated. In addition to these existing published data, Poettman and Dean" have reported the water content of propane in the three-phase region (only the propane-rich liquid and the vapor phases were studied) and Michels, et al.15 have reported the solubility of methane in water at pressures to 6800 pounds per square inch at 77°F and at pressures to 1500 psia at temperatures to 300°F. It has been shown12,14 that the presence of water will materially affect the phase equilibrium of hydrocarbon systems. In order to make experimental studies on the quantitative effect of the presence of water in naturally-occurring hydrocarbon systems, it is desirable to have data available on binary hydrocarbon-water systems. A program is underway at this laboratory to determine the phase relations of the hydrocarbon-water systems. Initially the investigation will be limited to binary systems with water as one of the components. Later ternary and complex systems will be investigated and reported. EQUIPMENT AND ANALYTICAL PROCEDURE Apparatus In order to avoid a description of the methods employed in each subsequent paper, a description of the apparatus and the analytical procedure will be given here. The apparatus is shown schematically in Fig. 1. The numbered items in Fig. 1 represent the high pressure valves. The equilibrium cell is of the totally enclosed type, with a volume of 550 cubic centimeters. The cell is mounted in an air bath which in turn is mounted on pillow blocks and connected to a rocking mechanism so that the cell and bath will oscillate approximately 30 degrees above and below the horizontal at 35 oscillations per minute. The air bath is heated by two resistance heaters. The first or primary heater is 250 watts and is controlled by a thermoregulator; the second heater is of 500-watt size and is manually controlled to aid in bringing the cell to equilibrium temperature. Air circulation in the bath is accomplished by means of a fan. the shaft of which is concentric to the heaters. The walls of the bath are insulated with 2-in. thick blocks of 85 per cent magnesia. Temperature observations are made with three calibrated thermocouples. One couple is sealed in a well provided within the equilibrium cell, and is used as the criterion of the cell being at the equilibrium temperature. The other two thermocouples are located on opposite sides of the cell to indicate temperature uniformity within the air bath. The thermoregulator, used in conjunction with a relay, gives a variation in the temperature of the air in the bath of plus or minus one degree Fahrenheit. However, since the equilibrium cell weighs approximately 55 pounds, the

Jan 1, 1950

By N. F. Dyson, T. R. Scott, M. R. Thornber, W. E. Ewers, M. Bussell

Leach liquors derived from the processing of nickel ores are generally highly contaminated and contain appreciable free acid. Methods are described for obtaining a commercial grade of concentrate from such solutions using pyrrhotite as the seed material to abstract nick- el, cobalt, etc. from solution. At temperatures in excess of 160° C., recoveries of 99% can be obtained from contaminated solutions where the free acidity is as high as 0.5 M in sulphuric acid. At lower temperatures down to 80° C., high recoveries can also be obtained either by adding H2S to the system with appropriate adjustment of the free acidity or by using "activated" pyrrhotite or artificial FeS in the system without prior addition of H2S. The methods are applicable to liquors derived from either oxide or sulphide ores, and the products are suitable for smelting or other known processes used to obtain pure metals. The mechanism of the reaction appears to vary with the operating temperature, and the results ye therefore discussed in the light of electron probe and optical microscopic studies.

Jan 1, 1973

By K. A. Natarajan, I. Iwasaki

The effect of poisoning on the behavior of platinum electrodes in redox potential measurements in metallurgical systems was studied in the presence of such inorganic surfactants as cyanide and sulfide and such organic surfactants as dodecylammonium acetate, trimethyldodecylammonium chloride, potassium ethyl xanthate, and potassium diethyl dithiophosphate (Aerofloat®). These chemical species represent, more or less, typical constituents encountered in leaching, flotation, and sewage treatment systems. Triangular wave voltammetry was used as the experimental technique to study the nature of poisoned surfaces. Among the species studied hydrogen sulfide and dodecylamine were found to form a resistant surface film affecting charge transfer. Platinum electrodes appeared to have a weaker tendency to adsorb sulfide species in alkaline pH ranges, while cyanide, xanthate, and dithiophosphate affected the normal electrode behavior differently. Possible methods of reactivation of a poisoned electrode by mechanical cleaning are suggested.

Jan 1, 1974