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By D. S. Dinsmoor

Boron, estimated to comprise about 0.001 percent of the earth's crust (Fleischer 10), as an element is never found free in nature, although its compounds are found in many localities. the borates are the most important. Sassolite (B(OH)3) and boracite (Mg6C12B1406), non-borates, are-of-minor importance. The crystal structures of most natural borates are still unknown. A classification based solely on the ratio of boron to the total number of cations has been devised (Palache 28). This classification divides the borates into four, sub-groups; anhydrous borates, hydrated borates, borates containing hydroxyl or halogen and compound borates. Only four or five minerals of the hydrated borates group have ever been used commercially. In more recent years, the sodium borates have comprised all but a 'small fraction of all borates used. Borax, the hydrated borate compound, is the most important of all boron compounds. It has been used so long and so often that the layman often confuses borax and boron and, applies the terms synonymously.

Jan 1, 1958

By John C. Machisak

INJURY DATA and experience at, coal mines in the United States for 1953 and 1954 are presented in this publication with a minimum of interpretation and comment because of the numerous tables required to afford detailed comparisons between the 2 years. Corresponding tables for 1953 and 1954 follow in consecutive order under the following general sections: (A) General injury experience: Tables 1 to 11: Contain current data on number of fatal and nonfatal injuries, frequency and severity rates, and average severity and time-loss rates. (B) Selected injury data: Tables 12 to 85: Contain current data on causes of injuries, distribution of injuries by part of body injured, days of disability, extent of hand and machine loading, experience by employment and production groups, and various other operating factors and physical conditions related to the occurrence of injuries at the Nation's coal mines.

Jan 1, 1958

By R. L. Smith, J. L. Rutherford

ALTHOUGH considerable effort has been devoted toward the determination of the mechanical properties of pure metals, it is extremely difficult to compare the results of such work. This is because of differences in method and type of test, grain size, heat treatment, and purity of material. There is very little information on the properties of most of the high melting point reactive metals with purities greater than 99.9 pct. Previous evidence concerning the tensile properties of unalloyed metals show that: body-centered-cubic metals are brittle at low temperatures; face-centered-cubic metals remain ductile; some hexagonal metals remain ductile, others become brittle. It may be that traces of impurities decrease the low temperature ductility of the body-centered-cubic lattice. This would suppose that a body-centered-cubic lattice free from impurities would exhibit nearly the same ductility as a face-centered-cubic structure. The present investigation has been an evaluation of the tensile properties of zone refined iron in order to determine whether higher purity material than that previously evaluated behaves differently. Experimental Procedure In this investigation, high purity iron was zone purified using the floating zone method.' The starting stock was obtained from two sources. The first,

Jan 1, 1958

By W. N. B. Armstrong

CORROSION of metals, for the purpose of this talk, may be divided into two general classes, namely, atmospheric and chemical. Atmospheric corrosion is caused by the natural agents -water, air, salt, and temperature -as well as by the agents arising from industrial operations which pollute the atmosphere. Chemical corrosion affects metals in refineries and chemical plants where severe conditions exist due to .acids, alkalies, salts, solvents, gases, ?steam, etc. A special condition is encountered on road equipment and motor vehicles due to the large amounts of corrosive salts which are used on our roads in the winter. Exposure to corrosive conditions such as those referred to above causes metal to be destroyed and, therefore, it has to be protected. The non-metallic or organic coatings used to protect the metal are themselves destroyed ultimately by these same conditions. Since all types of organic coatings do not have the same kind and degree of resistance to degradation, a particular kind of -coating must be used for a particular set of conditions in order to obtain the maximum benefit. In ?addition to the above mentioned agents, organic coatings are degraded ?by sun-light, which is probably the severest single factor in the breakdown of organic coatings exposed outdoors. We can divide organic coatings, in a general way, into the following classes: (1) Conventional coatings, and (2) Special coatings.

Jan 1, 1958

By R. D. Russell, R. M. Farquhar

SOTOPIC tracers have become an important aid in following the progress of chemical processes in the laboratory. It has recently been found possible to utilize a system of naturally existing iso-topic tracers to obtain information about the geological history of lead ores. Common lead, such as is found in lead deposits, is a mixture of four stable isotopes having atomic weights 204, 206, 207, and 208. Of these, the last three are identical with the lead isotopes produced as stable end products of the radioactive decays of uranium and thorium: the first, lead-204, is not known to be produced on the surface of the earth by any process. Since uranium and thorium Occur in the surface regions of the earth in amounts comparable with lead, and since the half-lives of uranium and thorium isotopes are of the same order as the age of the earth, they produce the radiogenic lead isotopes in amounts comparable to the amount of nonradiogenic lead present. Every significant exposure of a sample of lead to uranium and thorium will therefore lead to the permanent alteration of the lead isotope ratios in that sample. It is this unique property of lead that serves as a means of tracing the history of a lead sample in terms of its contacts with the radioactive elements. If lead from a lead mineral has been analyzed with a mass spectrometer, the measured isotope ratios are determined entirely by the isotope ratios of primeval lead, which are identical for all minerals, and by the particular history of the sample. It follows that for samples from any particular geological area, observed differences in the isotopic composition are enough to distinguish different geological histories. An illustration of the qualitative application of this statement is given in Table I by analyses of some galenas from the western Cordillera. Samples from deposits in Pre-Cambrian sediments have very different lead isotope ratios from those of the ores in the Paleozoic sediments. Although the two types are associated closely geographically, it is apparent that they have had quite different histories and have probably been emplaced at quite different times, as the ideas outlined in the following section suggest. Even when applied quantitatively, a lead isotope analysis can never indicate a unique history of any lead sample. However, it greatly restricts the choices available and combined with other geological and geochemical data can lead to a much better understanding of the genesis of lead ores. General Character of Lead Isotope Variations: Early isotopic analyses of common leads by Nierl showed that geologically younger leads were generally richer in isotopes of masses 206, 207, and 208, with respect to that of mass 204. This regularity of measured lead isotope ratios can be easily observed by plotting each of the ratios Pb207/Pbm and Pb205/ Pb204 against the ratio Pb206/Pb204. In both graphs the points lie scattered closely about a well defined mean curve. It was immediately supposed that this regularity resulted from the growth of all leads from a common primeval lead present at some time, To, early in the earth's history. Lead in the outer part of the earth would become continually enriched in the radiogenic isotopes as a result of the uranium and thorium intimately associated with it. The subsequent extraction of some of this lead and formation of a lead mineral free of the radioactive parents provide samples of lead existing in the earth at the time of mineralization, T. Younger leads in general will be richer in the radiogenic isotopes because they have been associated with uranium and thorium for a longer time. Then lead ratios would be given by the formulae: (Pb206/Pb204)YTPb^/Pb204) +f "(u201) kdt T (Pb207Pb204)r = (Pb208/Pb204)T0 + J (U295/Pb204) k' dt T (Pb208/Pb204) t = (Pb208Pb204 + J (Th204) A." dt [1] where A, A', and A" are the decay constants of U238, U285 and Th232. Summaries of measurements of radioactivity of surface rocks, such as given by Faul,2 are of limited

Jan 1, 1958

By L. M. Pidgeon, P. G. Thornhill

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,'"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. lengtn of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of ¼ in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10o to 15oC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press Operating at a temperature of 140°C

Jan 1, 1958

By D. E. Wolfson, D. A. Reynolds, F. W. Smith

IN 1948 the U. S. Bureau of Mines began a three-phase program to evaluate the extent and quality of U. S. coking coal: 1) a factual appraisal of known recoverable reserves in beds of mineable thickness, 2) a study of preparation characteristics, and 3) a study of carbonization properties. A previous paper presented the methods used in assessing reserves.' Although this investigation is only partly completed, data on coking properties of the Pittsburgh district coals are now available. The results are presented in this article. When coals are selected for manufacture of metallurgical coke more factors must be considered than for any other major use, as no basic industry requires coal of such high quality and uniformity. This is particularly true in the Pittsburgh district, where blast furnace practice is based on use of cokes from high quality coals. Although it is true that inferior coals are carbonized in other industrial areas, both here and abroad, the Pittsburgh coals are the best economically obtainable in the required tonnages, even though they are not the most desirable for metallurgical use. In the general evaluation of suitability of coals for coke making, particular attention is given to: 1) reserve, 2) ash and sulfur content, 3) inherent properties of forming strong, well fused coke, 4) expanding characteristics, and 5) blending properties. Items 1 and 2 are covered in detail in the first two phases of the survey, and coking behavior is considered in items 3 through 5. Problems is Coal Evaluation: Although not all coal beds of immediate or potential use to the coking industry in the Pittsburgh area have been tested for their coking properties, enough tests have been made to permit certain generalized statements. Virtually all the coals that will be used in this district are from the Appalachian region, and except for high oxygen coals from outcrops or stripping operations, they are coking coals. Hence the evaluation problem is not so much that of distinguishing between coking and noncoking coals as attempting to measure quantitatively differences in the coking and expanding properties of the better coking coals. Quantitative differentiation between good coking coals, is complex, since differences in their coking abilities are frequently of about the same magnitude as the precision of the test. Small-scale tests are generally unsuitable for measuring these slight differences, and there has been gradual acceptance of pilot-scale tests. Test Methods Employed: All the data reported here were obtained in two units known as the Bureau of Mines-American Gas Association (BM-AGA) carbonization apparatus and the sole-heated expansion oven. The BM-AGA unit, which consists essentially of a cylindrical steel retort about 18 in. diam and 26 in. high, carbonizes enough coal (180 lb) to allow evaluation of the coke by standard methods of the American Society for Testing Materials. The BM-AGA carbonization procedure and methods of testing the gas, liquid, and solid products have been described.' Expanding characteristics of the coals were determined in the sole-heated expansion oven," wherein the coal charge, heated from the bottom only, is carbonized under a constant applied force and the linear expansion or contraction is measured. Although results in this oven have never been quantitatively correlated with the expansion behavior of coals in conventional slot ovens, they are useful in assessing expansion behavior. In this report discussion will be confined to results obtained from these pilot-scale units, although the following data are available for most coals: proximate and ultimate analyses, free swelling index, agglutinating value, and plasticity. Sources of Coals Tested: In selection of coals for coke manufacture, economic considerations are as important as quality, and each coke plant balances these two factors to meet requirements of the most satisfactory coke at lowest price. Although these economic factors may in some instances outbalance small differences in coke quality, they are usually specific to each coke plant and cannot be given in any general statement. Recognizing that coal and plant operating costs are beyond the scope of the survey, the USBM evaluates the coking quality of various coals without regard to their competitive economic status. For the purpose of this article, coals of interest to the Pittsburgh district are arbitrarily defined as

Jan 1, 1958

By James Westfield

Uranium activity has introduced a comparatively new hazard to United States mining. In addition to the hazards common to all mines, uranium mines have a complex health problem of radiation damage. Like many new processes, radiation and nuclear energy can be made to serve man in many useful ways when properly understood and handled; but, like fire, gases, and electricity, their potential dangers must be known and respected, and appropriate precautions must be taken or death may result. Since 1950 the Public Health Service has been conducting basic investigations on exposure to radon and its daughter products and the effect of exposure upon the health of miners in uranium mines of the Western States. The Bureau of Mines assisted in several of these investigations, especially in mines on Indian lands. The studies have shown that a serious health hazard exists from radioactive exposure that might cause lung cancer if continued over a number of years. The Public Health Service report, Control of Radon and Daughters in Uranium Mines and Calculations on Biologic Effects,6/ shows that 55 percent of the uranium mines employing 64 percent of the miners had atmospheric concentrations more than five times the working level now accepted as reasonably safe for industrial exposures. Extensive control measures are necessary to reduce these concentrations to the suggested working level of less than 300 micromicrocuries of total radon daughter products per liter of air.

Jan 1, 1958

By J. G. Richardson, F. M. Perkins

Results and procedures are pre-cented covering a laboratory investigation of the effect of rate of water advance on the displacement of oil from clean water-wet sands. The experiments included water floods at atmospheric pressure with and without gas present over a range of flow rates from reservoir rates to rates ten thousand-fold higher. Water floods were also conducted at various rates at elevated pressure with no gas present. Other tests were made at elevated pressures by forming a free gas saturation by evolution of gas from solution in the oil before water flooding. Recovery of oil was found to be independent of the rate of water advance with or without gas present and independent of the pressure level of the water flood. A dimensionally-scaled model of a reservoir composed of a thick uniform sand was used to study the effect of rate on the tendency of water to underrun the oil because of the greater density of the water. Another model was used to study the effect of rate on the tendency of water to channel down the more permeable sand in a stratified reservoir composed of sands of diffierent per-meability in intimate contact. The effect of the presence of gas on the flooding conformance was studied with both models. The results obtained using these simple models provide a basis for predicting behavior in more complicated systems. INTRODUCTION In spite of the great amount of research on the flow of fluids in porous rocks, there still exists some disagreement as to the influence of the rate of water advance on the displacement of oil by water flooding. Various investigators have found that increasing the rate of water injection would decrease, increase, or have no effect on recovery of oil. One reason for this disagreement has been a lack of understanding of the effects of the capillary forces which influence the results obtained in the laboratory at low rates with short columns. Other causes of the disagreement have undoubtedly been inconstancy and uncertainty of the wetting properties of the porous media studied, inaccurate saturation determinations, and in some instances conclusions based on insufficient data. Capillary forces are involved in the displacement of oil by water in two ways. On the microscopic scale, the capillary forces control the dis- tribution of oil and water in the pore spaces of the sand. The magnitude of these forces is governed by the preference of the sand to be wet by water, the pore sizes and geometrical shapes, and the interfacial tension between the water and oil. On the macroscopic scale, differences in saturation at the flooding "front" when water displaces oil result in capillary pressure gradients. These gradients cause water to flow preferentially ahead of the front. In short laboratory columns at low rates, the front can span the entire column length. Also, at the outflow boundary the preference of sand to be wetted by water results in retention of water and a high water saturation in the region of the outflow face. This effect is commonly called the boundary effect.' The capillary pressure gradients which complicate the interpretation of flooding performance of short laboratory columns at low rates of water advance become negligibly small under certain conditions. The conditions where capillary pressure gradients are negligible are in long, homogeneous reservoir sands,' at high rates of water advance in short laboratory columns,3 and at any rate in laboratory columns as the residual oil saturation is approached. Thus, laboratory water floods, conducted

Jan 1, 1958

By Roy F. Abernethy

All samples tested showed some loss of heating value for the 5-month period under all 4 storage conditions. The losses increased as the time of storage increased, with the pan-storage samples showing somewhat greater losses than those in cans. The individual daily analyses for the first 2 weeks and the analyses every other day for the third and fourth weeks of storage vary within the approximate tolerance of the test for heating value. During the first 2 months of storage the changes in heating values were not Significant for the samples from Pennsylvania, Indiana, and Colorado. The Ohio coal indicated some loss by the end of I month, which increased to a value measurable with certainty by the end of 2 months. These data show that (1) small changes may occur even to samples in closed cans and (2) the laboratory sample should be handled as expeditiously as is practical until the analysis is completed. The statement by the ASTM that "If the B.t.u. determination is an important consideration in the sale of coal, the time elapsed between sampling and analysis shall not exceed 30 days,"3/ is quite adequate for 3 of the 4 coals tested. The change in the Ohio coal stored for 30 days is merely indicated and could not be determined with certainty by the techniques normally employed. The data on free-swelling indexes determined on can samples, after 30° C. air drying, show that only the Indiana coal lost more than one unit in free-swelling index number in 120 days. No significant changes were observed with the samples from Pennsylvania, Ohio, and Colorado in the 5-month period.

Jan 1, 1958

By Denton R. Wieland, Harvey T. Kennedy

The frequency of bubble formation is measured for oils from the East Texas field and the Slaughter field in cores from these fields. East Texas oil was also tested in a Slaughter core. The data checked previous results in that a definite supersatrtration may exist without the formation of bubb1es in periods of observation totaling 158 hours. Measured frequencies varied from zero at supersaturations below 14 psi to 3.1 bubbles/sec/ cu ft of rock at 40 psi supersaturation INTRODUCTION The formation of bubbles is essential in a solution gas-drive reservoir in the displacement of oil. In formations where the basic pore structure consists of fine pores or fractures connected to larger pores or crevices, bubble formation in the fine pores may be the most effective means by which the oil may be displaced, even if secondary methods are applied. The most efficient oil displacement would occur where at least one bubble would form in every pore. As the pressure decreased, the bubbles would expand, due to the gas diffusing into the bubbles, and displace the oil toward the lower pressure area around the wellbore. Kennedy and Olson' have shown that the total number of bubbles formed in a reservoir is primarily dependent upon the rate of pressure drop, the rate of diffusion of gas through oil, and surface area of the rock. The surface tension of the liquid and other characteristics of the rock may also exert an important effect, which would give a different frequency to different rocks and oils and various combinations of different rocks and oils. The purpose of this paper is to present frequency measurements on two rocks and two oils. A hydrocarbon liquid is at equilibrium with gas when it contains the maximum volume of gas in solution that it can have at the prevailing temperature and pressure. If the temperature is maintained constant and the pressure is reduced below the equilibrium pressure, the liquid is supersaturated to the extent of the difference in the two pressures until the gas comes out of solution as a free phase. As shown by previous work, and confirmed in the present investigation, the number of bubbles formed per second increases with an increase in supersaturation. Kennedy and Olson showed that a tenfold increase in the rate of pressure decline resulted in a tenfold increase in the number of bubbles formed per cubic foot of reservoir rock, e.g., for decline rates of 0.1, 1, and 10 psi/day, the number of bubbles formed per cubic foot would be 40, 400, and 4,000, respectively. For another hypothetical system, Stewart, Hunt, and Berry' estimated that for pressure declines of 0.1, 1, and 10 psi/day, the number of bubbles formed would be approximately 10, 100, and 1,000 cu ft of reservoir rock. Their value of bubbles formed is lower than given by Kennedy and Olson; however, the order of magnitude agreed satisfactorily. The rate of diffusion will also affect the number of bubbles formed. If the diffusion coefficient is high, the gas in solution in the oil surrounding a single bubble will tend to diffuse into the bubble rather than forming other bubbles. On the other hand, the formation of more bubbles will tend to occur if the diffusion coefficient is very low. In his thesis dated Aug., 1953, Wood" reports on the frequency of bubble formation in a system consisting of oil and rock from the Rangely field. In the present work, the apparatus of Wood was redesigned to allow greater precision, especially at low supersaturations, where bubble growth is slower, and detection is more difficult.

Jan 1, 1958

By John H. Nicholls

In this paper, Imperial Oil Limited reports briefly on the drilling by contract rigs of twenty-nine slim holes in the Virden, Smiley, and Souris Valley areas. The investigations showed that slim-hole penetration rates, as a result of careful control of drilling variables, can approach those achieved with 7 7/8-inch bits. It is concluded that slim-hole drilling is acceptable for development or exploratory work. Imperial also reports on the completion techniques and equipment that have been developed on twenty-seven tubingless 2 1/2-inch casing completions. Indications are that the method is economically desirable where excessive gas or water production is not anticipated.

Jan 1, 1958

By Hsun Hu

NOT much data are available in the literature on textures in cross-rolled metal sheets. Among the body-centered-cubic metals, a few investigators have studied the preferred orientations developed in cross-rolled and in subsequently annealed molybdenum specimens.1-4 Semchyshen and Timmons5 onstructed complete pole figures for the cross-rolled and subsequently annealed arc-cast molybdenum. They used the conventional photographic method. Similar data on cross-rolled iron are still lacking. In view of the fundamental importance of iron as a basic metal for magnetic alloys and many industrial steels, the present investigation was undertaken in an attempt to understand more about its properties. The material selected for the present work was of high purity, and the textures were determined by the Geiger counter spectrometer technique, which permits the construction of quantitative pole figures. Experimental Procedure The material used for this investigation was NRC (National Research Corp.) high-purity, gas-free iron. The total gas content (N2 + O2 + H2) given was less than 0.026 pct, and the carbon content, less than 0.005 pct. Spectrographic analysis of a 2 in. cast ingot showed the percentage of metallic impurities as 0.0004 pct Cu, 0.0002 pct Mg, 0.001 pct Mn, 0.01 pct Ni, and 0.006 pct Si. A 1 in. thick slice was cut off from the 2 in. cast ingot. It was hot-forged at 850 °C to destroy most of the cast structure. Surface scale was removed by milling the forged piece to a size 2 in. long, 1½ in. wide, and ¾ in. thick. After normalizing at 915 °C for 15 min, the piece was alternately cold-rolled 40 pct and annealed at 750°C in hydrogen to a final thickness of 0.165 in., with a resulting uniform grain size of 0.1 mm.

Jan 1, 1958

By F. W. Smith

To determine whether preheating coals before carbonization would improve the coking properties of the coals, particularly the weaker coking coals, 3 coals, 1 each from Illinois, Kentucky, and Pennsylvania, and a blend of the Illinois with a Pocahontas coal were preheated before testing for coking properties in the Bureau's BM-AGA pilot oven. The effects of preheating on the chemical and physical proper-ties of the coals and on the yields of carbonization products and strength of the coke produced from the preheated coals were determined, as were also the effects of bulk density, gaseous atmosphere, and residence time during preheating. Most benefit from preheating was found with weaker or oxidized coking coals, whereas the more strongly coking coals and blends showed little effect. Direct charging of preheated coal to the coke oven without cooling gave better coke, increased yield of tar, and decreased yield of gas. INTRODUCTION Although 94 percent of today's coal production comes from fields east of the Mississippi, the Eastern States have only about one-third of the Nation's recoverable reserves. West Virginia, which now produces more than any other State, has much smaller reserves than Utah, Colorado, and Wyoming.5/ However, the manufacture of iron and steel in Western States, which has increased greatly since World War I, is handicapped by the scarcity of high-grade coking coals, such as are plentiful in the Appalachian region. Unless a practical method of improving the cokemaking property of local coals is developed, ferrous metallurgical industries in the West must continue to use inferior coking coals and to pay high shipping charges for better coals.

Jan 1, 1958

By J. H. Wernick, D. Dorsi, K. E. Benson

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,'"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. iength of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10O to 15OC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press operating at a temperature of 146°C

Jan 1, 1958

By J. H. O’Dette

BLISTER formation on wrought aluminum products has been a matter of concern to aluminum fabricators for many years. The fact that blisters make their appearance during the final stages of fabrication means that much time and effort have been expended before it is evident that the material must be scrapped. This and the loss of production are ample reasons for embarking on a research program to find out more about blistering and possible methods of control. Many excellent papers on this subject have appeared in the technical literature in the last few years. In one of the more recent papers, Kostronl gives a fairly complete review of the problem of gas in aluminum and blistering in general. From the work of the various investigators, a general mechanism for the formation of blisters has evolved and may be summarized briefly as follows: Hydrogen gas is usually present in the cast ingot, in the atomic or ionic state, in excess of the solid solubility. At room temperature the gas atoms are relatively immobile, but at elevated temperatures they become mobile and diffuse to free surfaces where they associate to form molecules. If these free surfaces are discontinuities within the ingot then the associated gas molecules collect and build up considerable pressure until equilibrium is reached with the dissolved gas around the discontinuity. Since the solubility of the gas is proportional to the square root of the partial pressure it is evident that large pressures may be built up at the discontinuities. When the metal is rolled to sheet the pressure of the gas in these, discontinuities is sufficient to deform the surface of the sheet and form a blister, particularly when the strength of the material is reduced during the annealing. Although the mechanism of the formation of blisters was fairly well known, the actual impor- tance of the individual roles played by the gas and the discontinuities was not so well established that positive methods for control of blistering were at hand. It was the object of the investigation to learn more about the nature of the discontinuities giving rise to blistering and to develop methods of control. The investigation was carried out in three stages as follows: a) A study of the more commonly used methods of removing hydrogen from aluminum, such as fluxing and holding, and their effects on blistering. b) Location of the discontinuities giving rise to blistering. c) A study, by indirect methods, of the movement of gas in the metal and its effect on blistering, and the development of methods of blister control during fabrication. Removing Gas and Reducing Blistering by Fluxing or Holding-—The work of removing gas and reducing blistering by fluxing or holding was carried out on metal of Alcan 2s (1100) composition with an artificially high gas content. The high gas content was obtained by introducing water into the melt prior to casting; the water reacted with the aluminum forming A12O3 and hydrogen. The procedure was to raise the gas content by introducing water into an aluminum melt and using half the melt to cast one ingot immediately. The remaining metal was treated again with water to make up for the reduction in gas content during holding, while the first ingot was being cast, and then given a fluxing or holding treatment and cast into an ingot. Samples for gas determination were cast from the molten metal before and after the gassing operation; before, after, and during fluxing, and while casting. Samples were also cut from sections of the ingots. Gas determinations were made on these samples using the well known vacuum fusion technique. All ingots were hot rolled at 500°C to 0.250-in. slab which, in turn, was cold rolled to 0.040 in. sheet. The sheet was coiled and annealed for 2 hr at 500 °C and then cut into 5-in. squares which were inspected for

Jan 1, 1958

By P. E. Schauer

During the initial nine-year deple-tion of the McKamie-Patton pool gas-condensate reservoir, the pressure behavior and fluid analyses indicated pressure maintenance by gas injection would be attractive relative to continued pressure depletion. As a result, a gas cycling program was inaugurated in Aug., 1949, which has since maintained reservoir pressure. In order to evaluate the benefits of this program, the recoveries for natural depletion and for cycling followed by blowdown were determined by calculating the fractional balance of the molar quantities of vapor and liquid remaining in the reservoir and produced at the surface for various stages of depletion. The results of the investigation show theoretical ultimate recovery due to the cycling program will be 42 per cent greater than would be realized under pressure depletion type operation. INTRODUCTION The benefits of gas injection pressure maintenance programs in condensate reservoirs have been recognized and qualitatively described in several papers1-8 during the past 15 years. Some of these papers also describe methods for calculating the increased recovery realized from cycling; however, as a rule, hypothetical reservoirs were used as examples".'.. This paper presents an evaluation of the pressure maintenance program for the McKamie-Patton condensate reservoir and includes a description of the fractional balance method employed to determine the benefits. Reservoir Development and Characteristics The McKamie-Patton pool, Lafayette County, Ark., was opened in June, 1940, with production obtained from the oolitic Smackover lime at a depth of approximately 9,300 ft. The structure is an anticline 8 miles long by 1 to 2 miles wide, and is one of many productive Smackover structures in Southern Arkansas. Of predominant importance is the condensate-bearing gas cap portion of the reservoir, which covers approximately 4,000 acres, attains a maximum thickness of some 200 ft, and has an average thickness of 90 ft. Development of the cap was accomplished with 21 wells drilled on 160 acre spacing. An isopach map of the cap is shown in Fig. 1. In addition, an oil rim is present along most of the periphery of the pool. Production practice includes field separation of black oil, and a high pressure gathering system which carries total well stream from gas cap wells to a plant where condensate is separated and the gas is processed for recovery of natural gasoline, butane, and propane. Since the gas contains appreciable hydrogen sulfide, it is removed by amine contact, after which free sulfur is produced by the Claus process. Core analyses from 1,767 gas cap formation samples averaged 14.2 per cent porosity and 379 md dry air permeability. Connate water was restored on seven samples of gas cap rock by air-brine capillary techniques, from which the interpreted water saturation averaged 28.17 per cent. During the early life of the field, it was believed the recovery mechanism, based on several of the other regional Smackover reservoirs, might be a natural water drive. However, subsequent production and pressure history revealed that the gas cap would not be produced by water drive, but would behave as a closed reservoir. In this respect, during the nine-year period of natural depletion from initial production to Aug., 1949, the cap production of 84.3 billion

Jan 1, 1958

By W. H. Ode

In 1949 the Coal Committee of the Economic Commission for Europe, Geneva, Switzerland, established a Classification Working Party, to develop an international system for classifying coal. This project was necessitated by the increased trade in coal among various nations following World War II. Although national classification systems existed, they had been developed to cover the characteristics of domestic coals without reference to coals of other countries. Different terms for describing similar or identical coals in each nation caused confusion in evaluating coals shipped in international trade. Experts from Austria, Belgium, Bulgaria, Czechoslovakia, Denmark, the Federal Republic of Germany, France, Greece, Hungary, Italy, the Netherlands, Poland, Sweden, the Union of Soviet Socialist Republics, East Germany, the United Kingdom, the United States of America, and Yugoslavia participated in various stages of the classification work. Walter A. Selvig was appointed by the Bureau of Mines as the technical expert to represent the United States because of his experience in developing and standardizing methods of analyzing and classifying American coals. He served on the Classification Working Party until his retirement from the Bureau of Mines early in 1956. Extensive laboratory work was done in connection with the classification studies at the Pittsburgh Experiment Station of the Bureau of Mines.

Jan 1, 1958

By C. G. Dunn, K. T. Aust

SEVERAL studies1-10 have reported a type of grain boundary migration which occurs when a strained grain grows into an adjacent deformed grain during annealing. Beck and Sperry called this phenomenon strain-induced grain boundary migration, since the observed boundary movement, which takes place in a direction away from the center of curvature, is apparently motivated by the excess free energy of strain hardening. However, little information has been obtained on the detailed structural changes accompanying such grain boundary motion. The problem of driving force for strain-induced boundary migration was considered by Dunn and Daniels,' who used bent bicrystals of Si-Fe. They demonstrated that two grains of differing energy, in the form of subboundaries, behaved according to the concept that the low-energy grain would grow at the expense of the high-energy grain. Beck" reported experiments of Sperry for high-purity aluminum, which indicated that generally the particular grain of a pair which work-hardened more was invaded. The measure of work hardening here was

Jan 1, 1958

By R. A. Bergman, C. J. B. Fincham

THERMODYNAMIC properties of many high-temperature systems containing sulfur, such as slags, metal sulfides, and solutions of sulfur in liquid metals, have been studied by means of equilibration with known gas mixtures.'" This method presupposes a complete and accurate knowledge of the thermodynamic data for all possible components of the gas phase at high temperatures. However, a survey of the data available up to 1952 on the thermodynamics of gaseous sulfur species and compounds, by Richardson and Jeffes,' showed that there was considerable uncertainty in the values of the free energies of formation of S, SO, HS, and CS. In many cases, this uncertainty made it impossible to decide whether or not these species would form a significant proportion of the sulfur present in the gas phase in any given system. After the review by Richardson and Jeffes had been published, St. Pierre and Chipman6 measured, by an indirect method, the free energy of formation of SO. This also enabled a clear choice to be made among the three possible spectroscopic values for the dissociation energy of S2 into atoms10 thereby determining the free energy of formation of S from S2, and fixing the free energy of formation of HS more accurately" The main purpose of the present investigation was to measure the free energy of formation of CS, which was still in considerable doubt. For example, at 1600°C, it could be estimated to be +6 +25 kcal per mole,* most of the uncertainty being in the * Based on the dissociation energles of CS6 and S2,5 the heat of sublimation of graphite, and, the assumption that the entropy of formation of CS is the same as that of CO. value of the dissociation energy." A secondary purpose of the investigation was to determine more accurately the equilibrium sulfur pressures over dilute solutions of sulfur in carbon-saturated liquid iron. General Method Dilute solutions of sulfur in liquid iron, saturated with carbon, were brought to equilibrium at 1600" and 1800°C, with known gas mixtures consisting, initially, of A and CS2. After equilibrium had been reached, the melts were quenched and analyzed for sulfur. In the high temperature region of the furnace, an equilibrium was set up between the various possible sulfur species and compounds in the gas phase; namely, CS2, CS, S2, and S. (It can be calculated that the amounts of S6 and S, are negligible at these temperatures:) Morris and Bueh17 and Kitchener, Bockris, and Libermana had previously studied the corresponding

Jan 1, 1958