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By Harold Vagtborg

Equilibrium vaporization ratios were obtained for light hydrocarbons, nitrogen, carbon dioxide, and hydrogen sulfide in a reservoir fluid containing 35 mole per cent hydrogen sulfide. The data cover the range from 700 to 2500 psia at 154°F. The results of this study are compared with results obtained by other investigators on systems containing less hydrogen sulfide. When large amounts of hydrogen sulfide are present, the equilibrium vaporization ratios for ethane and heavier hydrocarbons are greater than the ratios for systems containing little or no hydrogen sulfide. Large amounts of hydrogen sulfide have the reverse effect on the ratios for methane. Routine PVT studies were performed on the reservoir fluid including flash and differential liberations of the dissolved gas. The pressure-volume relationships of the saturated fluid were also determined. It is shown that the use of published correlations on physical properties of reservoir .fluids can lead to gross errors when applied to systems containing large amounts of hydrogen sulfide. INTRODUCTION Equilibrium vaporization ratios for various components in naturally occurring crude oil and condensate systems have been reported in the literature.1,2,3,4 Recently, several papers have been published with emphasis on non-hydrocarbon components such as nitro- gen, carbon dioxide and hydrogen sulfide.5,6,7,8,9 The increased discovery of reservoir fluids having high concentrations of these non-hydrocarbon components, particularly hydrogen sulfide, has created a need for a further study of their phase behavior. Equilibrium vaporization ratios are known to vary with pressure, temperature, and overall composition of the system.'" It was anticipated that ratios for systems containing large amounts of hydrogen sulfide would differ from the ratios for systems containing small amounts of hydrogen sulfide. Therefore, the present work was undertaken in order to obtain reliable equilibrium vaporization ratios for the reservoir-fluid in question. PROCEDURE The procedure followed was evolved after considerable experimentation on methods of handling the very sour crude. It was found that drying agents (e.g. CaCl2 and CaSO4) absorbed an appreciable amount of hydrogen sulfide from the gas used to prepare the recombined samples. The concentration of hydrogen sulfide dropped as much as 10 mole per cent in a single pass through a 3-ft drying tube. It was also found that when undried gas was agitated with mercury in the PVT cell, a black scum, believed to be mercuric sulfide, was formed and the hydrogen sulfide content of the gas dropped several mole per cent. Because composition changes during a run could not be tolerated, separation of the mercury and sour fluid was necessary. In order to effect this separation, a stainless steel piston, equipped with Teflon O-rings, was placed in the PVT cell between the mercury and the sour fluid. This piston had to be constructed in three parts because

Jan 1, 1955

By W. David Menzie

An inventory of the mineral resources of a region is a most desirable basis for planning their systematic development. In the absence of appropriate samples upon which to base a reliable estimate of this inventory, investigators have resorted to a number of indirect approaches; the unit regional value concept forms the basis for one such approach. The produced resources of a region are a function of the inventory multiplied by the degree of intensity (some fraction between zero and one) of development of the resources. A convenient means of expressing this amount is to accumulate the weight and value of resource and to prorate the totals over the area represented by the unit sampled; i.e., weight and value per unit area or tonnes/km.2 and U.S. 1967 $/km.2. When this approach is used for the U.S.A., South Africa and Rhodesia the average value of (log.) U.S. 67$/km.2 for the states of the U.S.A. and South Africa are similar ($55,176 U.S.$67/km.2 and $52,538/km.2 respectively); whereas, Rhodesia is relatively underdeveloped (10,301 U.S.67$/km.2). On the other hand if the individual commodities are used as a basis for comparison, the U.S.A. shows the greatest diversity (67 commodities out of a possible total of 75) with South Africa next (50 commodities) and Rhodesia last with only 26 commodities. Since it is known that area and value are not simply related perhaps diversity is directly related to area. Again the kinds of commodities which have contributed the greatest value to the totals differs, with fuels (petroleum, coal and natural gas) predominating in the U.S.A. totals; whereas, South Africa and Rhodesia obtain their greatest contributions from gold, diamonds (S. Africa) coal and asbestos. In each case the greatest value of resources is produced from sedimentary rocks. As a somewhat different kind of example, consider a single resource (petroleum, the most valuable in the U.S.A.) over a large area (number of sampling units) the U.S.A. by state. Furthermore, assume that the model frequency distribution of the amount of petroleum (tonnes/km.2) is log normal. Then the present production fails to match the model first because 17 states (34% out of 50) have not produced petroleum. Of the remaining 33 states, Louisiana has produced the most (15,177 tonnes/km.2) and the frequency histogram is still skew. A spatial analysis of the distribution of the amount of petroleum by state shows that the samples (i.e., states) are not random; the non-producers and producers tend to cluster. It remains to be seen if this is indeed a true representation of the incidence of petroleum or is a function of the exploration philosophy currently in vogue.

Jan 1, 1977

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 J. S. UNGER

A LARGE proportion of the coke used is made in the by-product oven from the high-volatile coals mined in the adjacent district. At the beginning it was feared good by-product blast-furnace coke could not be made with our coals. By experimenting with various mixtures of coals, coking time, oven design, and coking temperatures, much has already been accomplished. The results show that a hard, dense coke, not easily broken by handling, can be produced. In its present state it is not all that could be desired, but it is being constantly improved. Such coke has been used alone as the fuel on several of the blast furnaces producing the highest daily production in the Pittsburgh district. Many of the coals in the Pittsburgh district when coked in the by-product oven yield a gas which contains a high percentage of sulfur, which is objection- able for many metallurgical operations. As this fuel is gradually replacing the ideal fuel, natural gas, which is becoming less plentiful, studies are being made of the best methods for purification. Some metallurgists believe sulfur to be a very injurious element in steel. Recent investigations by Government bureaus, scientific bodies and private firms, seem to indicate that a reasonable amount of sulfur may exist in steel without detriment. Without wishing to provoke any metallurgical controversy on the subject of sulfur, the fact remains that the daily purification

Jan 1, 1926

By H. L. Brunjes, G. B. Gould

The softening temperature of coal ash, as determined in the laboratory, has been used for years as an indication of the tendency of coal to form clinker and slag. It has not, however, provided an index of unfailing and complete reliability for forecasting the relative performance of different coals, even in the same plant and under the same conditions of operation. A large amount of investigation has been done in attempts to account for this, but practically all of this has been in the direction of studying the chemical constitution of coal ash. Much has been learned, but without much progress toward a better practical application of knowledge to the selection of coal. There has always seemed to be an important factor that eluded discovery. It has long been recognized that the ash-softening temperature as determined in the laboratory had one weakness, in that it represented the temperature at which a thorough mixture of the whole ash of the coal would melt, the mixing having taken place before the heal was applied. This does not, of course, simulate what takes place in practice. With certain exceptions, which will be noted later, almost all of the investigations that have been made, especially the chemical studies of coal ash, have likewise dealt with a mixture of the whole ash in the coal. The present investigation differs from these fundamentally in its approach to the problem. It started from the observation that some clinkering and slagging obviously takes place in a boiler furnace at temperatures below the laboratory-determined ash-softening temperature of the coal. Knowing that coal as it is shipped to market is a heterogeneous mixture of diverse mineral substances, each of which may act independently of the others in the initial stages of clinker and slag formation, it seemed logical to investigate separately the softening temperature of the ash in physically separable portions of the coal, and to determine the relative quantities of ash contributed by each portion. While the data are far from complete, covering as they do only a few coals, and while the conclusions to be reached from the data at this stage arc, in some measure, speculative, they are presented at this time because

Jan 1, 1940

By B. M. Larsen

AN increasing amount of attention is being paid to the possible influence of oxygen, in its several modes of occurrence in steel, upon some of the properties of the metal; but clearly investigations along this line are unlikely to yield significant results until reliable analytical methods for the determination of oxygen have been established. This paper presents some results of a study of an improved Ledebur method which aims to determine a definite portion of the oxygen; namely; that which presumably is present in diffusible form in the. solid steel. These more or less preliminary results lead us to believe that the oxygen so determined has some significance; their presentation at this time will, we hope, stimulate discussion of, and focus attention upon, certain rather neglected aspects of the problem. Considerable work has been done recently on methods of estimating inclusions and on the vacuum-fusion method for oxygen; with results which, however, are of somewhat questionable significance. It is commonly presumed that the oxygen in a bath of molten steel in a furnace is present partly as a separate phase consisting of suspended particles of oxides or silicates, partly in solution, the latter being probably the more important. Upon addition of a deoxidizer, it reacts with some portion of the dissolved oxygen and precipitates it as additional suspended particles; the oxygen not eliminated in this way, which remains in solution in the liquid steel, may be regarded indifferently either as dissolved oxygen or as dissolved FeO. When the steel is poured, some of the suspended particles rise towards the surface, others remain trapped in the finished steel, appearing as nonmetallic inclusions in amounts corresponding usually to about 0.01 to 0.03 per cent 02 in the steel. The dissolved oxygen may be partly eliminated as CO during freezing of the ingot, but some remains either in solution or in part precipitated as FeO. Finished steels may thus contain oxygen in several forms: (1) In non-metallic inclusions which are probably quite insoluble in the solid metal at all temperatures; (2) in solid solution which at lower temperatures may be supersaturated; (3) in FeO particles produced by relief of this

Jan 1, 1932

By G. B. Gould, H. L. Brunjes

The softening temperature of coal ash, as determined in the laboratory, has been used for years as an indication of the tendency of coal to form clinker and slag. It has not, however, provided an index of unfailing and complete reliability for forecasting the relative performance of different coals, even in the same plant and under the same conditions of operation. A large amount of investigation has been done in attempts to account for this, but practically all of this has been in the direction of studying the chemical constitution of coal ash. Much has been learned, but without much progress toward a better practical application of knowledge to the selection of coal. There has always seemed to be an important factor that eluded discovery. It has long been recognized that the ash-softening temperature as determined in the laboratory had one weakness, in that it represented the temperature at which a thorough mixture of the whole ash of the coal would melt, the mixing having taken place before the heal was applied. This does not, of course, simulate what takes place in practice. With certain exceptions, which will be noted later, almost all of the investigations that have been made, especially the chemical studies of coal ash, have likewise dealt with a mixture of the whole ash in the coal. The present investigation differs from these fundamentally in its approach to the problem. It started from the observation that some clinkering and slagging obviously takes place in a boiler furnace at temperatures below the laboratory-determined ash-softening temperature of the coal. Knowing that coal as it is shipped to market is a heterogeneous mixture of diverse mineral substances, each of which may act independently of the others in the initial stages of clinker and slag formation, it seemed logical to investigate separately the softening temperature of the ash in physically separable portions of the coal, and to determine the relative quantities of ash contributed by each portion. While the data are far from complete, covering as they do only a few coals, and while the conclusions to be reached from the data at this stage arc, in some measure, speculative, they are presented at this time because

Jan 1, 1940

By R. E. Hobart

The development of the Hauto power plant and the claims made by various engineers that electricity was more economical than steam for power purposes in and about the mines, led the Lehigh Coal and Navigation Co., in 1911, to conduct a test to ascertain the consumption of power used by a large steam hoisting engine. The question being one on which no reliable information could be found, and the opinion of various engineers differing to such an extent, it was decided that a test under actual operating conditions was necessary. This was arranged for at one of the collieries. The engine selected was 2 30 by 60-in. (76.2 by 152.4-cm.) piston-valve engine of modern type, and comparatively new. The boiler plant from which the hoist received its power was about 600 ft. (182 m.) from the engine, the latter being fed by a 10-in. (25.4-cm.) steam line insulated with magnesia pipe covering. Two batteries of the boiler plant, aggregating 1200 hp., were cut off and fed into a separate steam line leading direct to the hoist engine. Steam auxiliaries, consisting of feed-water pump and blowers, were fed by the boilers in test, and their consumption charged against the hoist. A barrel weighing device was installed, as it was felt that this would be the most accurate way of determining the consumption of water. The fuel, No. 3 buckwheat, was carefully weighed, and every precaution was taken to make the test accurate in every particular. The test was run for 1 week, or a total of 168 hr. A record was kept of the number of trips hoisted or lowered, and continuous indicator cards were taken. One particular set of cards was taken with the hoist operating balanced, and also with the hoist operating with no counterweight other than the empty cage, the coal in the car being weighed. The speed of the hoist was taken by means of a graphic recording instrument which registered the number of revolutions every 5 sec. From this record, speed-time curves were plotted.

Jan 1, 1918

By John E. Latz

QUICKSAND far below the surface, stopped two attempts by the Potash Co. of America to sink a third shaft to a potash bed that lies 1000 ft below the southern New Mexico desert. Virtually all methods of grouting were employed in the two failures without any indication of consolidation of the flowing sand. Sinking the South Shaft at the Carlsbad potash mine seemed an almost insurmountable task, until freezing was employed as a final resort. This process that proved to be the answer may be defined as "the sinking of a shaft by freezing, consists of the formation, in the water-bearing strata, of a large block of frozen ground in which it is possible to sink a shaft without danger of an influx of water, providing the ice-wall between the water outside and the shaft itself is strong enough to resist the hydrostatic pressure." Freezing Method Used Extensively in Europe Successful frozen ground shaft sinking projects had been completed in Europe, and Russel G. Haworth, resident manager of the Potash Co. of America, went abroad in search of the know-how needed for the New Mexico undertaking. The freezing process, with a history of two failures at the time, was first successfully employed by Poetsch in 1885 at the Houssu Collieries near Haine St. Pierre, Belgium. Poetsch contracted to sink the remaining 64 ft of an uncompleted shaft through water laden strata from a depth of 190 ft to a depth of 254 ft. This work was in progress until 1887. The freezing and sinking consumed more than two years. As a result of early failures, the process was not favorably received until soon after the turn of the century. The accurate prediction of success in a given application was made possible by the concerted effort and study of a group of European engineers. Means of accurate deviation measurement and control were devised, the nature and properties of frozen water laden soil (the ice wall) were investigated, a thorough and rational basis of refrigeration load calculation developed, and concurrently the efficiency and dependability of refrigeration machinery was greatly advanced. Numerous shafts in Germany, Belgium, France, and England today testify to the reliability and economical surety of the freezing method. Applied to the South Shaft, which is circular in cross-section and 15-ft diam, the freezing method consisted of drilling holes 350-ft deep, through the water bearing strata into impervious ground-the freeze hole pattern being concentric with the shaft and 31-ft diam. The holes were cased with pipe closed on the bottom end. Smaller tubes were placed inside these casings and connected to a header supplying chilled brine from a refrigeration plant. The brine descended in the tubing to the bottom of the hole and ascended through the annular space between the two pipes to the top of the casing; flowed into the return header and back to the refrigeration plant. Under these conditions, each of the freeze hole casings became surrounded by a cylinder of ice

Jan 1, 1952

By Gerhard Derge

THE extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: I. The reaction C + FeO -+ Fe + CO is rapid enough to make the correct sampling of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautio1 and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to A1203, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. 2. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. INDIRECT METHODS Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed more readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached, is not , well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the reactants than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equilibrium relations may be used more readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory means of determining oxygen for the calibration is felt keenly. For example, the statistical analysis of the relation between carbon and oxygen4 5 illustrates that even in a single plant wide variations exist under normal conditions of operation. Nevertheless, this is one of the best methods now

Jan 1, 1943

By D. R. Pratt, R. W. Hanks

The method of Caldwell and Babbitt for detennining Bingham plastic rheological constants from engineering pipe flow data has been erroneously used in many previous applications. A reanalysis of extensive pipe flow data from the literature is performed. Critical Reynolds numbers corresponding to the laminar-turbulent transition calculated from these data are found to agree with theoretically calculated values for the entire flow range studied. Similar agreement is found for the authors&apos; own data&apos; for flow of 10 slurries between parallel plates. The Bingham plastic model is shown to be a reliable representation of the flow of non-Newtonian slurries provided it is properly applied. If the Hedstrom number He = pD2 t0/?2 > 104, then the linear approximation method of Caldwell and Babbitt is invalid for pipe flow data obtained in systems of ordinary engineering interest, and the complete nonlinear form of the pipe flow Bingham plastic equation must be used in determining rheological parameters. INTRODUCTION Many materials of engineering interest must be handled and transported as slurries or suspensions of insoluble particulate matter in a Newtonian liquid. These suspensions frequently exhibit non-Newtonian rheological behavior which is reasonably well described by the simple Bingham plastic rheological equation1 Using this particular equation to describe the laminar flow characteristics of slurries was discussed at length by Caldwell and Babbitt2-4 who considered the flow of various clay slurries and sewage sludges. The model has since been used by many others.5-7 More recently the problem of predicting the laminar turbulent transition Reynolds number for Bingham plastic fluids has been treated8 for the case of flow in pipes. This paper points out errors which have existed in the analysis of Bingham plastic flow since the work of Caldwell and Babbitt2-4 and presents a reanalysis of the laminar turbulent transition calculatiod for Bingham plastic flow in pipes. In addition, new data obtained for flow of Bingham plastic slurries between parallel plates, both in laminar flow and in the laminar turbulent transition region, will be presented and compared with the theoretical analysis of laminar turbulent transition for flow between parallel plates. THEORETICAL ANALYSIS PIPE FLOW The mathematical analysisl-4 of laminar flow of a Bingham plastic fluid leads to the following equation. where q = <v>/R is a pseudoshear rate, rw is the wall shear stress Eo = r0/rw, r0 is the yield stress and 1 is the coefficient of rigidity or plastic viscosity from Eq. 1. Caldwell and Babbitt2-4 recognized that the quartic term in Eq. 2 was small compared to the other terms whenever 5, « 1, and that for large values of 7, a plot of Eq. 2 becomes linear. The slope of such a plot with rw as ordinate is 4? and the intercept is (4/3) ro. This approximation is illustrated schematically in Fig. 1. The shaded region between the true curve and the straight-line approximation near the origin represents the contribution of the quartic term. In principle, therefore,

By H. W. Hitzrot, R. H. Limons, L. V. Fegan

The testing of a new method for measuring pellet-bed temperatures in the traveling-grate or shaft furnace is presented in this paper. This method, using silver-palladium alloy wires as indicators, overcomes disadvantages existing in the methods based on the use of thermocouples which are costly and time-consuming. The authors have developed and tested a new method for measuring pellet-bed temperatures in the traveling-grate or shaft turnace through the use of silver-palladium alloy wires as indicators. This method overcomes the disadvantages of existing methods, which, based on the use of thermocouples, are generally costly and time-consuming. For example, in the case of the traveling-grate furnace, the installation of an instrumented pellet, together with its attached thermocouples, requires stopping the furnace, with resulting loss of production time. As for temperature measurement in the shaft furnace by the existing method, the movement of the shuttle-car feeder seriously interferes with both the actual insertion and the resulting distribution of continuously fed thermocouples. The authors have overcome these difficulties by using, as temperature indicators, a range of silver-palladium alloy wires that can be easily recovered, after firing at any desired location in a pellet furnace. Silver-palladium wires having specific melting points from 2000°F to 2500°F are enclosed in ceramic capsules. Each capsule is placed in a ni-chrome wire basket filled with a sample of green pellets, the baskets being the means for recovering the capsule after firing. After the encapsulated wires have been exposed to the firing cycle, the alloy wires are examined to determine the maximum temperatures attained by the pellet sample. This method gives accurate, rapid determinations of maximum temperatures attained during pellet induration in either the traveling-grate or shaft furnace The new method has the following advantages over existing methods: 1) it is less expensive; 2) no furnace downtime is required; 3) the testing units can, be made in quantity in advance; 4) measurements can be made in rapid succession at all desired locations; 5) measurements of maximum firing temperatures are more accurate; 6) on the basis of points 4 and 5, the new method gives a more reliable picture of the correlation of pellet quality, petrographic textures and maximum temperatures, thus providing a more effective quality-control tool. A disadvantage of the method is, of course, that the measurements are not continuous and only maximum temperatures are determined. TEST PROGRAM Preparation of Materials: CALIBRATION OF ALLOYS - In the following discussion the term "bead point" (see Fig. 1) refers to the temperature at which each alloy begins to melt and form a bead. Fig. 2 gives the bead point curve for silver-palladium alloys. Before the alloys are used in plant tests, the bead point of each alloy should be determined in the laboratory to verify the alloy compositions. Once a given alloy has been calibrated, it can be

Jan 1, 1965

By J. J. Jakosky

The strategic importance of the metallic minerals in our industrial economy, and the declining rates of discovery have focused attention on means of exploration for new mineral deposits. A consideration of exploration techniques leads to an attempt to evaluate the effectiveness of geophysics as a tool for mining exploration. One means of evaluation will be to compare the use of geophysics in petroleum exploration with its possible uses in mining. Geophysics in Petroleum Exploration During the past twenty years, the petroleum industry has established an effective exploration technique. Geology is the basic tool in those areas where reliable predictions can be made from surface conditions. In the other areas, where the geological studies are inadequate, they must be supplemented with geophysics or direct exploration, such as drilling. Since geophysical work is far less costly than any form of direct explbration, it is used almost exclusively as the means for obtaining the desired subsurface information. The geological and geophysical techniques are credited with locating sites which yielded one producer for three dry holes during the year 1947.&apos; For the wells located without geology or geophysics, there is a ratio of one producing well to sixteen dry holes. From these figures it is seen that the geological and geophysical techniques are more than four times as successful as the nontechnical exploration. It will be in order to consider further this ratio of one producer to three dry holes. The geophysical methods in use today† do not pretend to locate oil directly; their function is to locate anomalies or structures favorable for the accumulation of oil. For a producing oil well we must have not only structure, but also other favorable conditions, namely: petroliferous source beds, the required porosity and permeability in the reservoir rocks, an impermeable cap rock over the reser- voir, and the necessary water or gravity drive to force the oil into the bore hole. Since the geophysical work can only detect and sometimes delimit the anomaly, these other necessary conditions can be determined only by direct exploration. The success of modern geophysical work in locating and limiting the structure itself is remarkably high, probably over 95 pct accurate. Geophysical work renders an important service in the delineation of the structurally unfavorable areas and their elimination from the drilling phase of the exploration program. When attempting to locate any material of scarce occurrence in the earth, it is of paramount importance to know where not to dig. This elimination of barren areas is the least appreciated but is of great economic importance. For illustration, the difference between one producer to three dry holes, and one producer to sixteen dry holes, represents a saving of thirteen drilled wells, which would require an expenditure many times the cost of the geophysical work that might have revealed the nonfavorable structural conditions. The percentage of geophysically-located wells necessarily will continue to increase in the statistics of future years, as the search for oil is extended

Jan 1, 1950

By J. E. Lawrence

Copper-decorated lattice disorders in silicon have been analyzed by electron transmission microscopy, chemical etching, and P-N junction reverse current measurements before and following different gettering treatments. Lattice disorders acted as the nucleating sites for copper precipitation. Copper precipitates in silicon resist chemical etching, absorb electron beams more than silicon, and cause excess reverse currents. Totally gettered disorders will chemically etch rapidly, be transparent to electron beams at extinction contrast, and not contribute to excess reverse currents. Three different gettering procedures were performed to determine the effectiveness of different EXTRANEOUS metal contamination can alter the minority carrier lifetime and resistivity of bulk silicon as well as cause excessive reverse currents in semiconductor devices. Previous workers have reported such activity for gold,1,2 copper,&apos;-* iron,&apos; and rnanganese.2,5 Gettering is a method employed to render these impurities electrically inactive. However, some property of the junction-degrading metals prevents gettering procedures from being wholly reliable. The comparative effectiveness of gettering with different agents has been the topic of earlier publications.2,3,6-11 Two mechanisms for gettering metallic impurities have been proposed: the distribution coefficient mechanism by Thurmond and Logan7 and the compound formation mechanism by Goetzberger and Shockley.2 Both of these models evolved from data gettering mechanisms. First, phosphorus was allowed to enter a protective SiO2 film but remain away from the Si-SiO2 interface to test the effectiveness of the compound formation gettering mechanism. Second, phosphorus was allowed to enter the backside of silicon wafers to test the effectiveness of the lattice strain gettering mechanism. Finally, nickel was diffused into the backside of silicon wafers to test the effectiveness of the distribution coefficient gettering mechanism. In each case, copper precipitates dissolved as a result of the gettering treatment. Tightly packed precipitates will resist gettering more than loosely packed copper precipitates. acquired by the electrical analyses of gettered semiconductor materials. An electrical analysis, however, cannot identify the fate of the gettered metals. The radiotracer technique has recently been applied to determine the redistribution of metals following different gettering treatments.3,9,10 The spatial resolu tion of the radiotracer technique prevented the analysis of metal precipitates which contribute to the excessive reverse currents of P-N junctions. The gettering processes employed by the earlier workers, almost without exception, allowed the gettering agent to enter the silicon lattice. This procedure makes it quite difficult to differentiate between the distribution coefficient and the compound formation mechanisms. The metallographic analysis of gettered copper precipitates discussed in this work supplements the earlier work by obtaining direct evidence of silicon lattice defects decorated with copper before and following different gettering treatments. The effectiveness of a process which restricts the gettering agent, phosphorus, to a dielectric film and thus away from the silicon lattice is discussed in addition to the ef-

Jan 1, 1969

By John Chipman, Theodore B. Winkler

In order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and. abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chip-man,3 dealt with the simplest possible slag system that would resemble those found in the basic ope), hearth—the slag system consisting of CaO-MgO2-SiOz-FeO. (Taylor&apos;s rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemis- try of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, SiO2, FeO, Fe2O3, P2O6, MnO, Al2O3 and CaF2, but not all of the slag samples contained all of these components at one time. Review of Literature Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Krings,4 von Samson-Himmelstjerna,6 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution . Ratios

Jan 1, 1947

By Theodore B. Winkler, John Chipman

In order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and. abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chip-man,3 dealt with the simplest possible slag system that would resemble those found in the basic ope), hearth—the slag system consisting of CaO-MgO2-SiOz-FeO. (Taylor&apos;s rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemis- try of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, SiO2, FeO, Fe2O3, P2O6, MnO, Al2O3 and CaF2, but not all of the slag samples contained all of these components at one time. Review of Literature Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Krings,4 von Samson-Himmelstjerna,6 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution . Ratios

Jan 1, 1947

By Shiro Ban-ya, John Chipman

Using the same experimental method previously described, the activity of sulfur in a number of quaternary and more complex liquid iron alloys at 1550oC is determined. A "cross-product term zj.zk is determined for each of the quaternary alloys to take account of the mutual effects of the combinalion on the indi-vidual contributions to In 5 The interactiotl coefjicienls delermined for ternary solutions and cross-pvoducl coefficierlts from the quaternary systems are used to estimate the activity coefficient of sulfur in more complex alloys. OUR recent papers 1,2 have described new determinations of the activity of sulfur in Fe-S binary and Fe-S-j ternary solutions, but the practical applications of these data require the estimation of activity of sulfur in more complex systems. Previously, Sherman and chipman3 devised an approximate method for calculating the activity of sulfur in complex systems by summing the contributions to the logarithm of the activity coefficient of each element in the alloy. This procedure is more successful, as one of us has pointed out,4 when the concentration variable is taken as zs = ns/(nFe — nS t CLJ~ nj) rather than the conventional atom fraction x~ = nS/(nF, + nS + Enj). In the former definition, which is based on analogy to interstitial solutions, the value assigned to uj is normally +1 for metallic and -1 for nonmetallic elements." In addition, however, the effects of mutual interaction between alloying elements must be considered for the accurate estimation of the activity of sulfur in more complex systems. The purpose of this investigation has been to devise a more reliable method for estimating the activity coefficient of sulfur in nmIticomponent iron alloys. The measurements were carried out on some quaternary systems Fe-S-j-k for combinations of silicon, chromium, nickel, cobalt, molybdenum, and tungsten. Manganese was not included since the experimental method has been found unsatisfactory for volatile, sulfide-forming elements. The experimental method was the same in every detail as described previously. 1,2 The concentrations of sulfur, silicon, chromium, and copper in the quenched metals were determined by chemical analysis but those of nickel, cobalt, molybdenum, and tungsten were calculated from charged amounts. Iron sulfide was included in the charges in amounts estimated to furnish approximately the final sulfur content. CALCULATION W2 have shown2 that when zs and zj are the concentration variables in a ternary Fe-S-j solution the logarithm of the activity coefficient S = a~/zg is a linear function of the variables as and aj defined as follows:

Jan 1, 1970

By Cyril Wells, Robert F. Mehl

The diffusion of carbon in gamma iron plays an essential role in many metallurgical processes. In carburizing, in graphitizing, in homogenizing, in the formation of pearlite from austenite, and in other processes, migration of carbon in gamma iron occurs.1&apos;2 A full understanding of the rate at which these processes occur obviously requires a knowledge of the rate of diffusion of carbon. In carburizing, for example, the depth of carbon pentration is determined by the carbon concentration in solid solution at the surface, and by the rate of diffusion inward of the carbon. Until reliable data on the rates of diffusion of carbon are available it is unlikely that a full quantitative description of this process will be obtained. In the formation of pearlite from austenite, the segregation of carbon and alpha iron from the austenite obviously requires the diffusion of carbon; the rate at which pearlite nodules grow is evidently controlled at least in part by the rate of diffusion of carbon; it is unlikely that we shall understand the factors that determine the rate of growth unless data on rates of diffusion of carbon, and the variation of these with composition, grain size, and temperature are available. Accordingly it was decided: (1) to determine, more accurately than hitherto, the diffusion coefficients of carbon in austenite over a wide temperature and a wide concentration range, (2) to study the influence of grain size and impurities on this diffusion coefficient, and (3) to study the effect of manganese and nickel on the rate of diffusion of carbon in the austenite of manganese and nickel steels, respectively; the influence of carbon on the rate of diffusion of manganese and of nickel will be made the subject of later papers. The rate of diffusion of carbon in gamma iron has been studied by Runge3 by Tammann and Schonert4, by Bramley and co-authors,5-14 and

Jan 1, 1940

By W. R. Hicks, J. E. Pollock, E. Camp

In the oil-refining industry, steel comprises by far the greatest proportion of the materials used in construction work, but with an enormous number of alloy steels and nonferrous alloys available, and a greater knowledge of their properties and corrosion resistance, a substitution first in the "hot spots" and then in locations of moderately severe corrosive conditions will be made as the greater expense can be justified. In new construction work, advantage is taken of the experience already gained and appropriate materials used, whether for high temperatures and pressures demanding additional strength or for corrosive conditions. The locations, however, where equipment in operation constantly requires replacement will soon become evident, as will the necessity for replacement in more resistant materials, if considerable down-time is to be avoided. In what direction and how far to go in the matter of alloys then becomes a question of the highest importance. Obviously, any replacement with more costly material must be justified economically by the promise of longer life, thereby saving both material and installation costs besides the reduction of loss of production. Where the equipment is overcapacity and a regular schedule of cleaning periods is in force, the last item frequently must be ruled out and justification made on the basis of the first two only. Installation of material that will outlast the remainder of the equipment and have no recovery value must also be avoided; this is particularly important in temporary construction or in old equipment that will soon become obsolete. Test Methods Either one of two methods or a combination of both, in the absence of reliable data in similar services, may be adopted to determine to what extent replacement with other, and perhaps more expensive, materials is justified. A unit may be constructed incorporating different metals or alloys so that comparative service may be obtained under the same service conditions; this has been applied in many instances, such as condenser and tank construction, but the opportunities for inspection may be few and

Jan 1, 1935

By Cyril Wells, Robert F. Mehl

The diffusion of carbon in gamma iron plays an essential role in many metallurgical processes. In carburizing, in graphitizing, in homogenizing, in the formation of pearlite from austenite, and in other processes, migration of carbon in gamma iron occurs.1&apos;2 A full understanding of the rate at which these processes occur obviously requires a knowledge of the rate of diffusion of carbon. In carburizing, for example, the depth of carbon pentration is determined by the carbon concentration in solid solution at the surface, and by the rate of diffusion inward of the carbon. Until reliable data on the rates of diffusion of carbon are available it is unlikely that a full quantitative description of this process will be obtained. In the formation of pearlite from austenite, the segregation of carbon and alpha iron from the austenite obviously requires the diffusion of carbon; the rate at which pearlite nodules grow is evidently controlled at least in part by the rate of diffusion of carbon; it is unlikely that we shall understand the factors that determine the rate of growth unless data on rates of diffusion of carbon, and the variation of these with composition, grain size, and temperature are available. Accordingly it was decided: (1) to determine, more accurately than hitherto, the diffusion coefficients of carbon in austenite over a wide temperature and a wide concentration range, (2) to study the influence of grain size and impurities on this diffusion coefficient, and (3) to study the effect of manganese and nickel on the rate of diffusion of carbon in the austenite of manganese and nickel steels, respectively; the influence of carbon on the rate of diffusion of manganese and of nickel will be made the subject of later papers. The rate of diffusion of carbon in gamma iron has been studied by Runge3 by Tammann and Schonert4, by Bramley and co-authors,5-14 and

Jan 1, 1940