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By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th'rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling' in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By J. S. Kasper, R. M. Waterstrat

IN view of the recent findings of a pronounced ordering of atoms in s phase alloys containing elements of the first long row of the periodic table (and including molybdenum),l it is of interest to resolve the question of ordering for s phases containing second and third-row elements. Examples of the latter have been provided recently by Greenfield and Beck2 and two of them, Re-Cr and Ru-Cr, would appear to be favorable for a study of ordering by X-ray diffraction methods because of the considerable differences in the scattering factors concerned. In addition, s phase is found to occur in the Os-Cr system, where the difference in scattering factors is even larger. Accordingly, X-ray powder intensities have been measured in an attempt to learn the nature of the ordering, if any, in these three v alloys. Since there is no reported work on intermediate phases in the Os-Cr system, an exploratory investigation was made in this system, and it was found that, in addition to the s phase, the phase with the A-15 or ß-W structure also occurs. Specimen Preparation—The alloys were prepared by compressing mixed powders of —200 mesh size and sintering in an atmosphere of pure dry hydrogen. All alloys were rapidly cooled from the annealing temperature to room temperature in a stream of cold dry hydrogen in a water-cooled chamber. Table I lists the sources and purities of the starting materials, as well as the details of processing for each of the alloys investigated. Intermediate Phases in the Os-Cr System—In the absence of information on intermediate phases in the Os-Cr system, it was suspected that this system would resemble that of Ru-Cr, where a s phase, RuCr2,2 and a phase with the A-15 structure, RuCr3,3,4 have been identified. Both these phases were found in the Os-Cr system and at compositions

Jan 1, 1958

By J. D. A. Morrow

THIS discussion relates to the distribution of coal under the direction of the U. S. Fuel Administration beginning Apr. 1, 1918. At that time a definite method of ' controlling and directing distribution was put into effect. Prior thereto, although some of the machinery utilized was in operation, especially in the few weeks immediately preceding Apr. 1, distribution had not been effectively and comprehensively organized. The writer was called to the Fuel. Administration by Dr. Garfield about the. first of February, 1918, to assume general direction of the distribution of coal for the Fuel Administration, to develop the general plans, and to obtain practical men to assist in this work and in carrying through the program finally devised. A study of the situation and conferences with the Fuel Administrator and leading men in the business made it plain that it would- he necessary to begin at the bottom, measure the undertaking, develop plans to meet the need thus shown, and build an organization to effect the distribution required. This work had to be done under war pressure in the midst of a bad coal shortage. The successful performance of such a task is always primarily a matter of putting competent men in the right places and giving, them the power and opportunity to function properly together. In the Distribution Division of the U. S. Fuel Administration, the men who were chiefly responsible for whipping plans into practical form and then for carrying out these plans were A. W. Calloway, of Baltimore, President of the Davis Coal & Coke Co., who served as the Director of Bituminous Coal Distribution; S. Lovell Yerkes, of Birmingham, Alabama, Secretary of the Grider Coal Sales Agency, who assumed general charge of distribution while the new plans and organization were being perfected and then became the Assistant Director of Bituminous Coal Distribution; Warren S. Blauvelt, of Detroit, who was Director of Coke Distribution; A. S. Learoyd of New York, Director of Anthracite Distribution, in connection with the Anthracite Committee, consisting of Joseph

Jan 3, 1919

By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE large difference in the X-ray scattering factors for molybdenum and manganese makes the o- phase in the Mn-Mo system an interesting one to study with respect to ordering of the atoms. Such a study has been carried out using data obtained from a powder sample, and the resulting evidence for ordering in this compound is presented here. It is not possible, of course, to obtain all the details of structure for a u phase from powder data only. Most difficult of all would be the determination of precise atomic parameters. There is reason to believe, however, that the atomic parameters do not vary greatly in the different s'S and that the precise values obtained from one s structure would then allow decisions as to the ordering of atoms to be made when there is a large difference in scattering factors. In particular, the powder intensities for Mn-Mo s are for the most part in good agreement with those observed for Co-Cr, for which single crystal studies have been made by the authors.' There are a few marked discrepancies in the intensity comparison of the two s's, and these cannot be removed by adjustment of the parameters. They are interpreted as resulting from a more pronounced effect of ordering of the atoms. Accordingly, the parameters of Co-Cr s' have been used for the calculations of the Mn-Mo intensities. For Co-Cr, the space group is D4h14-P4/mnm with atoms in the following positions: 1—2 in (b); 11—4 in (f), with x=0.1031; 111—8 in (i), with x= 0.3713 and y=0.0370; IV—8 in (i), with x=0.5662 and y=0.2396; and V—8 in (j), with x=0.3160Y and y — -0.250. The unit cell is tetragonal, with an==9.10A and cn=4.74A for the Mn-Mo u phase studied here.

Jan 1, 1955

By Arthur F. TQggQrt

THE approximate status of education in ore dressing in 1871 is reflected by Rossiter W. Raymond in an article written at that time presenting the curricula and descriptions of the laboratories at the various mining schools in the United States. For the most part, the curricula in which ore dressing was taught were for mining engineering. They comprised courses in geology, mining, and pyrometallurgy about equal in point or credit weights; a short course in ore dressing, and a somewhat longer course in assaying; and courses in surveying, hydraulics, power, and strength of materials-all superimposed on a broad foundation of physics, chemistry, and mathematics. Some curricula contained a fair content of the humanities. Then, as now, the emphasis on fundamentals was greater in the older colleges and universities. The report on the Columbia School of Mines, then relatively young, emphasized that a large percentage of its students were college graduates. As technical and scientific knowledge grew, first metallurgy and then geology were set up as separate curricula. So far as curriculum designation is con-

Jan 1, 1947

By John J. Cioston

THE steadily rising flood of gold production from all parts of the world has created an avalanche of rumors regarding the stability of the present price of this metal. Markets have been unsettled from Johannesburg to London from New York and Toronto to Melbourne, despite repeated denials from, American and British authorities of any immediate intention to alter the price. Various economists and financial writers have blossomed forth with predictions that the price would be set at the old level of $20.67 per oz.; some have even been so brash as to state That a price of $15 would be necessary to bring production within control. These effusions, based entirely upon monetary theories and with no regard to production costs, serve to confuse rather than clarify the situation.

Jan 1, 1937

By D. L. Katz

The Oklahoma City Wilcox sand, discovered on March 26, 1930, has produced 394 million barrels of crude oil and 819 billion cubic feet of natural gas as of July I, 1941. The 100,000-bbl. wells, pressures of 2600 lb. per sq. in., and flows of "Wilcox" sand caused exciting moments in the early life of the field. Today the reservoir is substantially at atmospheric pressure and produccs 75,000 bbl. of crude oil daily through 466 pumping wells. Early estimates of the initial crude-oil content of the "Wilcox" sand1 indicated that about 600 million barrels of crude oil would remain after the pumping wells ceased to produce economically. The Oklahoma City Wilcox Secondary Recovery Association was organized in March 1939, to study the possibilities of recovering a portion of this oil. Only a very brief summary of the information available can be presented in a paper of this nature. Some simplifications and generalizations are necessary to give the over-all picture in SO short a space and statements made may not apply to a specific well or small area. Since the area under consideration by the Association is that north of the south line of section 22-11-3, some information will be presented for areas A, B, C, 1, 2, 3 and part of 4 of Fig. 2, and some will be for the entire Wilcox zone west of the fault. This paper is essentially an abstract of an engineering report made by A. D. Small, B. T. Murphree, M. C. Sons and the author for the Oklahoma City Wilcox Secondary Recovery Association on Sept. 5, 1940. Some information is taken from a report to the Association by C. V. Sidwell on March I, 1940, and some data are from a recent report by A. D. Small. It gives a brief history of the Wilcox zone, estimates of the initial oil contents of the reservoir, present conditions in the reservoir, and probable results from several programs of "secondary recovery." History of Wilcox Zone The Wilcox sand lies on the flank of the general structure, as shown by cross section of Fig. I2,3,4 and areal map of Fig. 2. The sand is of Ordovician age and is composed of well assorted, rounded sand grains with no apparent cementing material. The loose texture of the sand is shown by the enormous quantities of sand production from the wells and from the soft cores. The productive sand varies from zero thickness on the east to 220 ft. maximum and to zero thickness on the west because of water. The development of the pool4 as dependent upon drilling restrictions within the city limits, which accounts for the spacing of drilling operations listed in Table I by years. In 1931, areas I through 7 of Fig. 2 were open for drilling with the exception of some west-edge properties, and all wells drilled before Feb. I, 1935, were in this portion of the field. Nearly all wells drilled from 1933 to 1037 were in areas A, B and C. Since 1939, the newly drilled wells have gradually enlarged the producing area toward the west in the northern portion.

Jan 1, 1942

By D. L. Katz

The Oklahoma City Wilcox sand, discovered on March 26, 1930, has produced 394 million barrels of crude oil and 819 billion cubic feet of natural gas as of July I, 1941. The 100,000-bbl. wells, pressures of 2600 lb. per sq. in., and flows of "Wilcox" sand caused exciting moments in the early life of the field. Today the reservoir is substantially at atmospheric pressure and produccs 75,000 bbl. of crude oil daily through 466 pumping wells. Early estimates of the initial crude-oil content of the "Wilcox" sand1 indicated that about 600 million barrels of crude oil would remain after the pumping wells ceased to produce economically. The Oklahoma City Wilcox Secondary Recovery Association was organized in March 1939, to study the possibilities of recovering a portion of this oil. Only a very brief summary of the information available can be presented in a paper of this nature. Some simplifications and generalizations are necessary to give the over-all picture in SO short a space and statements made may not apply to a specific well or small area. Since the area under consideration by the Association is that north of the south line of section 22-11-3, some information will be presented for areas A, B, C, 1, 2, 3 and part of 4 of Fig. 2, and some will be for the entire Wilcox zone west of the fault. This paper is essentially an abstract of an engineering report made by A. D. Small, B. T. Murphree, M. C. Sons and the author for the Oklahoma City Wilcox Secondary Recovery Association on Sept. 5, 1940. Some information is taken from a report to the Association by C. V. Sidwell on March I, 1940, and some data are from a recent report by A. D. Small. It gives a brief history of the Wilcox zone, estimates of the initial oil contents of the reservoir, present conditions in the reservoir, and probable results from several programs of "secondary recovery." History of Wilcox Zone The Wilcox sand lies on the flank of the general structure, as shown by cross section of Fig. I2,3,4 and areal map of Fig. 2. The sand is of Ordovician age and is composed of well assorted, rounded sand grains with no apparent cementing material. The loose texture of the sand is shown by the enormous quantities of sand production from the wells and from the soft cores. The productive sand varies from zero thickness on the east to 220 ft. maximum and to zero thickness on the west because of water. The development of the pool4 as dependent upon drilling restrictions within the city limits, which accounts for the spacing of drilling operations listed in Table I by years. In 1931, areas I through 7 of Fig. 2 were open for drilling with the exception of some west-edge properties, and all wells drilled before Feb. I, 1935, were in this portion of the field. Nearly all wells drilled from 1933 to 1037 were in areas A, B and C. Since 1939, the newly drilled wells have gradually enlarged the producing area toward the west in the northern portion.

Jan 1, 1942

By Robert J. Linney

In the latter part of the year 1943, it was decided to experiment with diamond-drill blast holes in the Old Bed magnetite mine at the Mineville mines of the Republic Steel Corporation, in sections of the ore body where vertical dimensions were large and where development for sublevel bench stopes had already been done. Other possibilities of application for this drilling method were in the reclamation of old floors and pillars in the pitching folds of the Lower Old Bed ore body and in the reclamation of large vertical pillars in the "21" Bonanza-Joker ore body. The cross sections and views of the two ore bodies will show the conditions to which the diamond-drill method has been applied. The Lower Old Bed magnetite ore body is lenticular and dips approximately 30° toward the southwest and strikes generally southeast and northwest. An intensely folded structure, which pitches generally on an axis approximately at right angles to the strike, is continuous from the uppermost old workings down to the present bottom of the mine, and probably continues with depth. On successively lower levels this folded structure becomes greater in vertical dimensions and the two folds are closer together in a horizontal dimension. As shown in Fig. I, this folded structure gives to parts of the ore body considerable vertical dimensions, which provide areas that were developed for sublevel bench stoping above a slushing drift, as shown in Fig. 2. It was in one of these previously devel-oped sublevel bench stopes, No. 26 on the 1185-ft. level, that the diamond-drill blast-hole method was applied for mining the upper sublevel. The lower sublevel was underhand-bench-drilled to the finger raises of the scram drift below. The roof of this stoping area began to break and spall on the lower sublevel, causing the roof to become inclined. Along the hanging wall of the stope this reached an elevation about half way between the two sublevels. A smooth schistose seam in the hanging wall causes the ore to break away freely. Therefore, if bench mining had been carried on in the upper sublevel, a dangerous condition of poorly supported benches would have resulted. When the drillers were slashing across the sublevel te footwall and hanging wall to make a bench, spdlling roof of the opening below would probably have carried away part of the bench, and would have left a dangerous place in which to continue underhand benching. A 6 by 8-ft. raise had been driven between the lower stope and the upper sublevel about 200 ft. from a manway. It was decided to use this raise for a starting cut and to arrange holes as shown in Fig 3, so that a slot would be opened across the ore body between the footwall and hanging wall. This slot would then be used for the purpose of breaking into the ore, by blasting vertical rings of holes drilled at right angles to the axis of the pitching folds as nearly as possible. Layouts of this slot drilling and the rings adjacent are

Jan 1, 1946

By Ervin E. Underwood

IT has been recognized for many years that dis-persed particles have great value in raising the creep resistance of metallic alloys. In fact, some of the most successful high-temperature alloys owe their superiority to this factor above all others. A recent observation by Glen1," indicates that even better high-temperature resistance to deformation results in alloys capable of two successive precipitation reactions. The ramifications of this finding are of great interest. Unfortunately, our understanding of the reasons for such notable improvements has not kept pace with technical developments. In an effort to uncover some of the basic facts governing strengthening by particles, a program was initiated at the Battelle Memorial Institute with the primary goal of comparing creep strengths in single-phase and two-phase (precipitating) alloys. The effects of precipitation from solid solution on the creep properties of alloys are generally such that the resistance to creep is increased. However, if alloys are heat treated to different degrees of hardness before creep testing, it is often found that those possessing the maximum hardness initially do not necessarily have the maximum creep resistance. Depending on the stresses and temperatures involved other structures may prove more desirable. Considerations of the above nature indicate the importance of defining the initial state of the alloy. Here, it was decided to start with quenched single- phase alloys in which precipitation and creep deformation proceed concurrently. Equipment and Experimental Procedures Preparation of the Specimens—Four 25 lb ingots were prepared from 99.999 pct Cu and 99.996 pct Al to compositions of 1, 2, 3, and 4 wt pct Cu. Spec-trographic and chemical analyses are listed in Table I. After heat treatments and intermediate reductions, the alloys were cold rolled to 1/8 in. thick sheet. The final cold reductions amounted to 50, 40, 20, and 10 pct for the 1, 2, 3, and 4 pct Cu alloys, respectively. The specimens for creep testing were machined into tensile flats 7 in. long, 3/4 in. wide (at the shoulders), and 1/8 in. thick. The reduced sections were 1/4 in. wide and 21/2 in. long. After heat treatments at 540°C to an ASTM grain size of 1 1, the specimens were quenched into water at room temperature, then electropolished in a glacial acetic acid and perchloric acid solution. The gage marks were Knoop impressions placed 2 in. apart on the reduced sections. Blanks of 1 x 1 in, were cut from the same sheets for the age hardening runs and were given the same grain size heat treatments. The specimens and blanks were stored in a refrigerator at —40°C until needed for testing. Creep Measurements—Creep tests were conducted in a constant temperature room which was maintained at 26° ±1°C. A split-type, hinged, vertical-tube furnace was mounted on a horizontal track so that the specimen could be enclosed suddenly. Thus, it took about 15 min for the specimen to come within 5°C of the test temperature. The temperature variation along the specimen was controlled to about

Jan 1, 1958

By Alfred H. Bell, George V. Cohee

Illinois produced 146,788,000 bbl. of oil in 1940, or nearly 11.0 per cent of the total for the United States, and ranked fourth among the oil-producing states. Its production was only slightly less than that of Oklahoma, which produced 11.5 per cent of the national total. Illinois' production in 1940 represents an increase of 55 per cent over the previous year, when it amounted to 94,912,000 barrels. The development of the Devonian limestone in the Salem and Centralia fields is largely responsible for the increase in production during 1940 Production from the Devonian limestone in these two fields was estimated to be 36,698,000 bbl., or 25 per cent of the state's total production (Table I). The increase in production during June, when the state's daily average production attained a peak of 518,200 bbl. for the week ending June 29, was due to the Devonian production at Centralia (Fig. I). The initial production of the best Devonian wells in the Centralia field was as high as 12,000 bbl. in 24 hr. Daily average production in IIIinois for 1940 was 400,000 bbl. of oil, but actually daily production fluctuated widely during the year. At the beginning of 1940 daily production was approximately 330,000 bbl. During the first hali of the year it in-creased irregularly to the peak in June mentioned above and as the prolific Devonian producing areas were drilled up, the state's daily production declined rapidly during July and continued to decline, although more slowly, until the end of the year, when the daily production was approximately 325,000 bbl. The daily average production per well in the new fields at the end of the year was approximately 40 bbl. (Fig. I). Oil from the Devonian was also produced in the Bartelso field, Clinton County, the Sandoval field, Marion County, and the Irvington field, Washington County, bringing the estimated total production from the Devonian limestone to about 26 per cent of the state's total production, The remainder was obtained largely from the Mississippian system. About 2 per cent of the total was from Pennsylvanian and Ordovician strata. The decline in the Devonian limestone production has been so rapid that the 1941 output from this system will probably be only a small fraction of that of 1940 unless large new reserves are discovered. The "Trenton" (Ordovician) limestone has been tested in two wells in the Centralia field and both were small oil producers at a depth of about 4000 it. The "Trenton" also was found productive in the Salem field at a depth of 4500 ft. (Table 5). The initial production of the discovery well, which was completed shortly after the end of the year, was 130 bbl. on pump. Other wells drilled early in 1941 had initial productions averaging 172 barrels. The outlook for 1941 is for a continuation of drilling activity in Illinois, but at a declining rate (Fig. I, upper curve). The most active area at the end of 1940 was in the deep basin area in Wabash, Edwards, White, and Hamilton Counties.

Jan 1, 1941

By Alfred H. Bell, George V. Cohee

Illinois produced 146,788,000 bbl. of oil in 1940, or nearly 11.0 per cent of the total for the United States, and ranked fourth among the oil-producing states. Its production was only slightly less than that of Oklahoma, which produced 11.5 per cent of the national total. Illinois' production in 1940 represents an increase of 55 per cent over the previous year, when it amounted to 94,912,000 barrels. The development of the Devonian limestone in the Salem and Centralia fields is largely responsible for the increase in production during 1940 Production from the Devonian limestone in these two fields was estimated to be 36,698,000 bbl., or 25 per cent of the state's total production (Table I). The increase in production during June, when the state's daily average production attained a peak of 518,200 bbl. for the week ending June 29, was due to the Devonian production at Centralia (Fig. I). The initial production of the best Devonian wells in the Centralia field was as high as 12,000 bbl. in 24 hr. Daily average production in IIIinois for 1940 was 400,000 bbl. of oil, but actually daily production fluctuated widely during the year. At the beginning of 1940 daily production was approximately 330,000 bbl. During the first hali of the year it in-creased irregularly to the peak in June mentioned above and as the prolific Devonian producing areas were drilled up, the state's daily production declined rapidly during July and continued to decline, although more slowly, until the end of the year, when the daily production was approximately 325,000 bbl. The daily average production per well in the new fields at the end of the year was approximately 40 bbl. (Fig. I). Oil from the Devonian was also produced in the Bartelso field, Clinton County, the Sandoval field, Marion County, and the Irvington field, Washington County, bringing the estimated total production from the Devonian limestone to about 26 per cent of the state's total production, The remainder was obtained largely from the Mississippian system. About 2 per cent of the total was from Pennsylvanian and Ordovician strata. The decline in the Devonian limestone production has been so rapid that the 1941 output from this system will probably be only a small fraction of that of 1940 unless large new reserves are discovered. The "Trenton" (Ordovician) limestone has been tested in two wells in the Centralia field and both were small oil producers at a depth of about 4000 it. The "Trenton" also was found productive in the Salem field at a depth of 4500 ft. (Table 5). The initial production of the discovery well, which was completed shortly after the end of the year, was 130 bbl. on pump. Other wells drilled early in 1941 had initial productions averaging 172 barrels. The outlook for 1941 is for a continuation of drilling activity in Illinois, but at a declining rate (Fig. I, upper curve). The most active area at the end of 1940 was in the deep basin area in Wabash, Edwards, White, and Hamilton Counties.

Jan 1, 1941

By E. J. Whittenberger

OVER the past two decades, the Cr-Ni stainless steels, popularly termed 18-8 steels, have been used in ever increasing amounts in the aircraft, automotive, chemical, transportation, and building industries.' The contribution of nickel to these steels is associated with its strong austenite forming tendencies which assure good hot and cold forming characteristics, and with its beneficial influence upon corrosion resistance, especially in oxidizing acids. The adjustment of the chromium and nickel contents has been used advantageously in controlling the rollability and the response of the mechanical properties of these steels to cold reduction. With the advent of the jet age and the government stockpiling of nickel, considerable emphasis has been placed upon the development of satisfactory low nickel or nickel-free substitute austenitic stainless steels, especially for nonmilitary applications.2 Fer-ritic 17 pct Cr (AISI Type 430) stainless steel has been effectively substituted for the austenitic grades in applications with mildly corrosive exposure. However, the limited formability and ferromagnetic behavior of this grade do not permit its satisfactory use for many applications. To achieve better formability in a nenmagnetic steel and conserve nickel, a number of low nickel substitute austenitic grades of stainless steel have been developed in recent years. In most of these steels, manganese and nitrogen have been substituted for a portion of the nickel content, for example, 17 pct Cr-4 pct Ni-6 pct Mn (AISI Type 201), 18 pct Cr-5 pct Ni-8 pct Mn (AISI Type 202), and 16 pct Cr-1 pct Ni-17 pct Mn, all of which contain approximately 0.15 pct N.1 The precipitation of ferrite when large ingots of these Cr-Ni-Mn-N steels are heated to temperatures high enough for conversion to slabs on conventional universal slabbing mills has seriously affected the hot workability of these steels. This has been especially true in the case of the 16 pct Cr-1 pct Ni-17 pct Mn (sometimes referred to as 15 pct Cr-1 pct Ni-15 pct Mn) composition." Because it is possible that little, if any, nickel will be available for nonmilitary stainless steel applications in the event of a national emergency, a need has existed for a nickel-free austenitic stainless steel containing hot and cold forming characteristics similar to 18-8 steels and corrosion resistance at least comparable to the 17 pct Cr ferritic steel. The aforementioned deleterious effect of ferrite upon the hot working characteristics of the 16 pct Cr-1 pct Ni-17 pct Mn, steel indicates the importance of establishing the austenite-austenite plus ferrite phase boundaries as the first step in the development of nickel-free or low nickel substitute steels. This paper presents the data collected in an elevated temperature constitutional study of the Cr-Ni-Mn-N system at the South Works of the United States Steel Corp. Experimental Procedure The 300 compositions used in the investigation were melted in a 26 Ib induction furnace and cast in 3 14 in. diam by 18 in tall hot-tcpped ingot mo1ds.

Jan 1, 1958

By Robert S. Dewey

Drilling in West Texas during 1942 was substantially less than in the previous year. In all. 1267 Wells were drilled, as compared with 2325 wells in 1941. Of these 1267 wells, 1052 oil wells, 10 gas wells and 69 dry holes were drilled in proven fields and 36 oil wells, one gas well and 99 dry holes were wildcat operations. Of the 36 wildcat wells completed as oil producers, 16 led to new field discoveries, three found new productive horizons in old fields, and 17 extended the productive limits of established fields. Where semiwildcat drilling took place along established productive trends, there was often no sharp demarcation between wildcat wells that extend field limits and normal development to fulfil lease obligations, other than the arbitrary classification of a well as a wildcat if it was drilled at a distance of 2 miles from a producing oil well. The dry hole drilled on the edge of a field may have proved a more hazardous operation than a semiwildcat drilled several miles from production but favorably located on structure. The percentage of successful wildcatting ranges from 26.5 down to 14 per cent, dependent upon the degree of inclusion of the semiwildcat operations. Irrespective of which figure was used, the West Texas area maintained its better than average exploratory position. No doubt a number of factors may have influenced the extent of the 1942 development. Among those arising from the economic dislocation attendant on the war effort, the following are worthy of note. Owing to inductions into the armed forces and shipyard competition for mechanically trained men, experienced drilling personnel was sharply reduced, thereby increasing drilling costs and well-completion hazards. Replacement labor has not met the same standard of responsibility or workmanship to which the oil industry has grown accustomed. Increased military consumption of aviation gasoline and other crude products, coupled with decreased domestic consumption of lower-octane gasoline, has stimulated the market demand for the types of sweet crude most readily processed with available refinery equipment to meet war requirements, and has depressed the market demand for the sour West Texas crudes. As a majority of the purchasers of West Texas crude normally ship a substantial portion of sour crude to the refineries on the Atlantic seaboard, the loss and diversion of tanker service between Gulf Coast and north Atlantic ports have further curtailed the market demand for this type of crude oil. As some purchasers of crude oil were able to move by pipe line their West Texas trunk-line capacity to Midwestern refining centers, they were not impelled to curtail purchases of West Texas crude. The varying ability of the purchasers of crude oil to market West Texas crude was reflected back to various fields to which they were connected, causing an unequal distribution of production as among fields and operators. The pipe-line runs from the West Texas-New Mexico area decreased from approximately 354,000 bbl. Per day in January to about 265,000 bbl. in December 1942. .Approximately 2,991,000 bbl. of West

Jan 1, 1943

By Robert S. Dewey

Drilling in West Texas during 1942 was substantially less than in the previous year. In all. 1267 Wells were drilled, as compared with 2325 wells in 1941. Of these 1267 wells, 1052 oil wells, 10 gas wells and 69 dry holes were drilled in proven fields and 36 oil wells, one gas well and 99 dry holes were wildcat operations. Of the 36 wildcat wells completed as oil producers, 16 led to new field discoveries, three found new productive horizons in old fields, and 17 extended the productive limits of established fields. Where semiwildcat drilling took place along established productive trends, there was often no sharp demarcation between wildcat wells that extend field limits and normal development to fulfil lease obligations, other than the arbitrary classification of a well as a wildcat if it was drilled at a distance of 2 miles from a producing oil well. The dry hole drilled on the edge of a field may have proved a more hazardous operation than a semiwildcat drilled several miles from production but favorably located on structure. The percentage of successful wildcatting ranges from 26.5 down to 14 per cent, dependent upon the degree of inclusion of the semiwildcat operations. Irrespective of which figure was used, the West Texas area maintained its better than average exploratory position. No doubt a number of factors may have influenced the extent of the 1942 development. Among those arising from the economic dislocation attendant on the war effort, the following are worthy of note. Owing to inductions into the armed forces and shipyard competition for mechanically trained men, experienced drilling personnel was sharply reduced, thereby increasing drilling costs and well-completion hazards. Replacement labor has not met the same standard of responsibility or workmanship to which the oil industry has grown accustomed. Increased military consumption of aviation gasoline and other crude products, coupled with decreased domestic consumption of lower-octane gasoline, has stimulated the market demand for the types of sweet crude most readily processed with available refinery equipment to meet war requirements, and has depressed the market demand for the sour West Texas crudes. As a majority of the purchasers of West Texas crude normally ship a substantial portion of sour crude to the refineries on the Atlantic seaboard, the loss and diversion of tanker service between Gulf Coast and north Atlantic ports have further curtailed the market demand for this type of crude oil. As some purchasers of crude oil were able to move by pipe line their West Texas trunk-line capacity to Midwestern refining centers, they were not impelled to curtail purchases of West Texas crude. The varying ability of the purchasers of crude oil to market West Texas crude was reflected back to various fields to which they were connected, causing an unequal distribution of production as among fields and operators. The pipe-line runs from the West Texas-New Mexico area decreased from approximately 354,000 bbl. Per day in January to about 265,000 bbl. in December 1942. .Approximately 2,991,000 bbl. of West

Jan 1, 1943

By W. Tempelaar Lietz

The Ten Section oil field is located in the San Joaquin Valley in Kern County, California. about 12 miles southwest of Bakersfield in Township 30 South, Ranges 25 and 26 East. The accumulation is in a low relief anticlinal dome and has a productive area of approximately 2,200 acres. Discovered in 1936 as a result of seismic work, it was the first field on the floor of the Valley to obtain production. It had a small primary gas cap, and since its inception has been produced by depletion with controlled withdrawal from the gas cap to minimize blowthrough. STRUCTURE AND STRATIGRAPHY The Ten Section structure is an elongated anticlinal dome with flank dips of only about 7 degrees. A map of the field, now fully developed, and a composite log are shown in Figs. 1 and 2. Contours shown on the map are on the top of the first zone, or Marker XA as indicated on the composite log. As shown, the field has a productive closure of only some 350 feet, and there apparently is no faulting in the reservoir. The productive measures in Ten Section are of Upper Miocene age and are known as the Stevens sand. They contain thin, irregular shale or siltstone streaks which vary considerably in stratigraphic position and thickness and apparently are rather discontinuous. As a result, individual sands and shales cannot be correlated over any appreciable area, which makes it difficult to subdivide the sand body into separate zones which are distinct throughout the field. However, there are two fairly persistent siltstone bodies that at the time of development were considered to divide the productive measures into three - zones. The first, or uppermost zone is productive over the entire field and has an average thickness of 180 feet, of which some 65 per cent is sand. It had a primary. gas cap in the crestal area with an areal extent of 930 acres. The second zone has a productive area somewhat smaller than the first zone, but it did not have any original gas cap. It has an average thickness of about 360 feet, of which 55 per cent is sand. The third zone has a very limited areal extent and a maximum productive thickness of 100 feet, of which 80 per cent is sand. Recently, a deeper oil accumulation, termed the "53" sand, was discovered, but it is not discussed in this analysis. In the first and second zones the water table was at 7,980 feet subsea, while in the third zone it was at 8,080 feet subsea. RESERVOIR CHARACTERISTICS Sand Characteristics The Stevens sand in Ten Section is hard and well consolidated, and numerous wells were cored for core analysis. Core data on four representative wells are shown, plotted beside the electric logs in Figs. 3 to 6. The average porosity is 20 per cent, with porosities ranging from 15 to 30 per cent. It is estimated, from cores taken with oil base muds, that the interstitial water content is about 40 per cent. The average weighted permeability is approximately 140, with measured permeabilities ranging from 10 to 3,000 md. As might be expected with practically no correlation of individual sand

Jan 1, 1949

By W. Tempelaar Lietz

The Ten Section oil field is located in the San Joaquin Valley in Kern County, California. about 12 miles southwest of Bakersfield in Township 30 South, Ranges 25 and 26 East. The accumulation is in a low relief anticlinal dome and has a productive area of approximately 2,200 acres. Discovered in 1936 as a result of seismic work, it was the first field on the floor of the Valley to obtain production. It had a small primary gas cap, and since its inception has been produced by depletion with controlled withdrawal from the gas cap to minimize blowthrough. STRUCTURE AND STRATIGRAPHY The Ten Section structure is an elongated anticlinal dome with flank dips of only about 7 degrees. A map of the field, now fully developed, and a composite log are shown in Figs. 1 and 2. Contours shown on the map are on the top of the first zone, or Marker XA as indicated on the composite log. As shown, the field has a productive closure of only some 350 feet, and there apparently is no faulting in the reservoir. The productive measures in Ten Section are of Upper Miocene age and are known as the Stevens sand. They contain thin, irregular shale or siltstone streaks which vary considerably in stratigraphic position and thickness and apparently are rather discontinuous. As a result, individual sands and shales cannot be correlated over any appreciable area, which makes it difficult to subdivide the sand body into separate zones which are distinct throughout the field. However, there are two fairly persistent siltstone bodies that at the time of development were considered to divide the productive measures into three - zones. The first, or uppermost zone is productive over the entire field and has an average thickness of 180 feet, of which some 65 per cent is sand. It had a primary. gas cap in the crestal area with an areal extent of 930 acres. The second zone has a productive area somewhat smaller than the first zone, but it did not have any original gas cap. It has an average thickness of about 360 feet, of which 55 per cent is sand. The third zone has a very limited areal extent and a maximum productive thickness of 100 feet, of which 80 per cent is sand. Recently, a deeper oil accumulation, termed the "53" sand, was discovered, but it is not discussed in this analysis. In the first and second zones the water table was at 7,980 feet subsea, while in the third zone it was at 8,080 feet subsea. RESERVOIR CHARACTERISTICS Sand Characteristics The Stevens sand in Ten Section is hard and well consolidated, and numerous wells were cored for core analysis. Core data on four representative wells are shown, plotted beside the electric logs in Figs. 3 to 6. The average porosity is 20 per cent, with porosities ranging from 15 to 30 per cent. It is estimated, from cores taken with oil base muds, that the interstitial water content is about 40 per cent. The average weighted permeability is approximately 140, with measured permeabilities ranging from 10 to 3,000 md. As might be expected with practically no correlation of individual sand

Jan 1, 1949

By R. G. Hudson, H. W. Paxton

The activities of iron and chromium in their binary system have been measured by the Knudsen orifice technique. The system is close to ideal at 1200- 1250 C with slight positive deviations. The effect of this on the liquidus and solidus is discussed and these are calculated for two limiting assumptions. The vapor pressure of pure iron, pure chromium, and one alloy is compared with that obtained by the Langmuir free-evaporation technique. The results agree, indicating a vaporization coefficient close to 1. HERE are no reported data on the thermody-A namic activity of iron and chromium in the solid portions of the phase diagram. It is generally assumed'.' that the liquid solutions of iron and chromium obey Raoult's law. Chen and Chipman" have inferred that the liquid solution obeys Raoult's law. The minimum' in the solidus-liquidus curves for the iron-chromium system shows that there are deviations from ideality in either the solid or liquid or both. Because of the importance of developing reliable techniques for obtaining activity data in alloy systems at high temperatures and of the data so obtained, an investigation of the activity of iron and chromium in the binary at 1200-1250 C was undertaken using the Knudsen cell. Experimental The apparatus and experimental procedures used in this investigation were described in a previous paper." The various materials used for the construction of the Knudsen cell are listed in Table I. The metal used for the determination of the vapor pressure of chromium was 99.9 pet pure, obtained from A. D. Mackay, Inc. The iron was obtained as electrolytic grade from Fisher Scientific Company. The Fe-Cr alloys used are shown in Table 11. The largest error and controlling factor in the accuracy in the experiments reported here are introduced because of temperature uncertainty, which is estimated to be ±3 deg C. This introduces an uncertainty of 26 pet in the measured pressure. Experimental Results and Calculations The vapor pressures of pure iron and pure chromium were calculated from the measurements by the Knudsen equation3 on the assumption that only Cr or Fe atoms were present in the gas phase. For metal vapors, at the high temperatures and low pressures involved in these measurements this should be a reasonable assumption. Whitman" corrections for the cells were made. The data and results of pressure calculations are presented in Table I, and are plotted in Fig. 1. In addition the heat of vaporization at the absolute zero, ?E°°, has been calculated for chromium. These calculations are summarized in Table 111. The data used in these calculations are as follows kelley13 (F° - E°°/T ) Speiser, et al H (F° - E°°/T ) 010 where F" — standard free energy at temperature T It was necessary to calculate the total pressure above the alloys from the total weight loss W of the cell during a run, because of the fact that all attempts to collect and analyze the chromium and iron vapor effusing from the cell in the apparatus available failed. The failure resulted from the re-

Jan 1, 1959

By Alec M. Crowell, J. W. Sanders

While the production of crude oil and condensate in South Arkansas increased only 1.7 per cent over the 1940 figure, complete utilization of gas produced with the oil and condensate, and heretofore wasted, was beginning to be evidenced. There were 26,229,264 bbl. of oil and condensate produced in South Arkansas during 1941, as against 25,790,380 bbl. for the year 1940. (Fig. I.) Since 1936, deep producing sands have been discovered in 18 fields and during that period only 40 per cent of the total state production has come from Upper Cretaceous formations while 60 per cent came from the Lower Cretaceous and Jurassic formations. The gas produced with crude oil and condensate from the latter formation contains large quantities of hydrogen sulphide, the maximum being 6900 grains per 100 cu. ft. in the Patton pool of Lafayette County. Gas Utilization During the latter part of 1940 and the early part of 1941, pilot plants were placed in operation to determine whether the hydrogen sulphide and deleterious material in South Arkansas gases could be removed economically. The Federal Government desired to build a large aluminum plant in the Ouachita Valley and was seeking cheap fuel for the generation of electricity. The fact that the gases were produced with appreciable quantities of crude oil and condensate made it available at a very low price, since the state's conservation law prohibits the flaring of any gas. As a result of these experiments the first large-scale unit for the processing of gases containing hydrogen sulphide was placed in operation on Sept. I, 1941. The plant is in the Magnolia oil field, Columbia County. It processes residue gas from the Shell Oil Company's gasoline plant in that field and also raw gas from the Village field, 6 miles east of the Magnolia field. The gas entering the desulphuri-zation unit is laden with approximately 1400 grains of hydrogen sulphide per 100 cu. ft. and is stripped to a content of 4 grains per 100 cu. ft. The capacity of the plant is 15 million cu. ft. of gas treated daily under a pressure of 160 lb. per sq. in. The cost of treatment, exclusive of depreciation, is appreciably less than I per 1000 cubic feet. Two other plants of much greater capacity have been announced and priorities have been granted, which should bring the total amount of gas treated to 150 million cu. ft. daily. The gas to be treated will have a maximum hydrogen sulphide content of 4500 grains per 100 cu. ft. and will be processed under a pressure of 600 lb. per sq. in. These developments are something entirely new in field practice for the industry. The fact that this heretofore wasted gas is available at very low cost has led to the location of some eight war industries within the state, in addition to the alu-minum plant. Recovery OF Sulphur The Susearch Corporation and the Southern Acid and Sulphur Co. placed in operation during 1941 pilot plants to de-

Jan 1, 1942