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By G. K. Williams

The continuous process of lead refining as at present operated at the Port Piric plant of The Broken Hill Associated Smelters Proprietary Ltd. was a development from investigations conducted in connection with the ordinary Parkes desilverizing process. It is not proposed here to discuss the theoretical considerations involved in continuous desilverizing because this aspect has already been dealt with in previous publications.1 Continuous Softening Process For economical desilverization of lead bullion, the bullion must first be subjected to refining processes for the removal of such impurities as copper, sulphur, arsenic, antimony and tin. This refining is effected by first drossing to remove copper and sulphur and then preferentially oxidizing the arsenic, antimony and tin from the bullion in the softening process. The theoretical basis of the continuous softening process is illustrated by the portion of the Pb-Sb-O ternary equilibrium diagram shown in Fig. 1. Under conditions of complete liquefaction, metal of the composition of softened bullion is in equilibrium with an oxide slag containing about 9 per cent antimony. In practice, of course, arsenic also is always present, and while the 0Pb-Sb-As-O quaternary system has not been worked out in detail, it has been found that in softening drossed smelter bullion of the composition produced at Port Pirie, arsenic is always reduced to 0.001 per cent or less when the antimony in the bullion is reduced to a satisfactory figure. In the operation of the continuous softening process, a two-phase system of a bullion low in arsenic and antimony and an oxide slag relatively high in those components exists in equilibrium. To this system is added continuously a bullion containing 0.2 per cent As and 0.8 per

Jan 1, 1937

By G. K. Manning, A. R. Elsea, A. B. Westerman

INTRODUCTION A CONSIDERABLE number of high-temperature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. At the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in Vitallium after various heat treatments. However, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases- might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chromium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja1 and Guertler2 indicated that cobalt and chromium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to '85 pct chromium undergo a transformation at 1200 to 1250°C. More recently, Wever and Haschimoto,3 Wever and Lange,4 and Matsunaga5 carried out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallographic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Matsunaga. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these exceptions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data and the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitallium by determining the diagram for the cobalt-chromium system. EXPERIMENTAL WORK For the convenience of the reader, the diagram as determined by the present investigation is presented in Fig g. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the, melting point for pure chromium is the

Jan 1, 1948

By Samuel E. Doak

The utilization of rotary kilns, of the well-known cement type, for the preparation of iron ores for the blast furnace, has become of considerable economic importance within the past 10 years in certain localities, notably those where the native ores are lean. Such kilns may be used simply for the agglomeration of ores too fine to be charged into the blast furnace (i.e., ores whose, loss in the dust catchers is excessive, and whose fineness is detrimental to the working of the furnace), or for the desulphurization of lump and fine ores the sulphur content of which does not exceed 6 or 7 per cent. The desulphurizing action can be combined with that of agglomeration provided the kiln is sufficiently large. Other processes have been developed for the same purpose, but while I am not able to draw a comparison between them by reason of lack of sufficient data, it is safe to say that the kiln, if properly dimensioned for the character of ore to be treated, will compare favorably in its results, both as to economy and quality of product, with any other process. It is not, however, as well adapted for the treatment of flue dust as is a sintering operation, on account of the large percentage of fine coke contained therein. Any combustible entering the kiln at its feed end renders the process very much more expensive and unsatisfactory on account of the difficulty of controlling the temperature, also because of the rapidity with which long "rings" form, due to the increased heat at the cooler end of the kiln. The greatest value of the kiln at present is in the treatment of pyrites cinder; that is, the residue from pyrites ore after the extraction of the greater part of the sulphur. This cinder, while high in iron content, has too much sulphur remaining in it to be allowed to form a large part of the blast-furnace burden, without further treatment. It will range in metallic iron from 42 per cent., representing a very low-grade cinder from a domestic pyrites, to 64 per cent. of the residue from the best Spanish ore, and the corresponding silica content will vary from the maximum of about 25 per cent. to 11/2 per cent. The residual sulphur depends largely on the type of burner used in the original desulphurization. In general, the leanest original ores retain the greatest amounts of sulphur. In modern practice the percentage of sulphur in the cinder is rarely as great as six, and seldom lower than one and one-half. Average analyses for iron, silica, and sulphur of the cinders that have come under my personal observation are as follows:

Jan 1, 1916

By Robert Mehl

A STUDY of the structures arising from the decomposition of the a solid solutions in the Cu-Zn and the Cu-Al systems is of peculiar interest in the study of the mechanism of precipitation from solid solutions. It is possible in these alloys, by varying the composition within the ß field, to precipitate from the same basic lattice phases having different lattice structures. It has been rather generally assumed heretofore that the type of structure originating from the decomposition of a solid solution-the Widmanstätten structure-is determined by the lattice structure of the parent solid solution alone. In the first paper of this series1 evidence was advanced which threw doubt upon this hypothesis; but definite proof of the correctness or incorrectness of the hypothesis should be forthcoming from a study of these alloys, for if the structures originating, for example, from the precipitation of the a phase from ß and of the -y phase from the ß in the Cu-Zn system should be shown to be crystallographically different, the hypothesis would necessarily be held as definitely disproved. Furthermore, the newer proposal enunciated in the first paper of this series-that the origin of the Widmanstätten structure lies in a cooperation between the lattice of the parent solid solution and that of the precipitate-which at present seems the only alternative hypothesis, would in such an event be given added weight. The work here reported shows that the Widmanstätten structures originating in the precipitation of the a phase from the a and in the precipitation of the -y phase from the ß in the Cu-Zn system are indeed crystallographically different; and incidentally presents some new descriptive information on the Widmanstätten structure from a more general point of view.

Jan 1, 1931

By L. F. Reinartz

FROM the earliest times when our prehistoric ancestors laboriously fashioned crude tools and weapons from meteoric iron until our day when we manufacture steel in 150-ton open-hearth furnaces, the production of iron and steel has played a dramatic and important role in the development of civilization. Progress in the science of refining iron ore into iron and steel was painfully slow for many centuries. The keen scimitars of Damascus, the broadswords of the English knights, the coats of mail of French knights, and the Iron Pillar of Delhi are well¬known examples of medieval metallurgical technique. Expense and the scarcity of raw materials originally limited the distribution of iron and steel products. It was not until the nineteenth century that a determined effort was made to adapt the use of steel to peaceful pursuits. The spectacular and rapid strides made in the manufacture of steel during the last hundred years were hastened by the invention during the decade 1860 to 1870 of two great steelmaking processes-the Bessemer and the open-hearth process.

Jan 1, 1936

By G. Gutzeit

METAL-ORGANIC INNER COMPLEXES AN inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity. 4,1-13 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime.) It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry,, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals.17 CHELATE-FORMING COMPOUNDS AS COLLECTORS In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxylamine (Cupferron) C6H5NO(=NONH4). Holman19 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-dioximes were generally selective collectors for nickel ores. Taurin NH2(CH2)2SO3H has been proposed for the concentration of oxidized lead ores.19 Diphenylthiocarbazone

Jan 1, 1946

By A. D. Brokaw

The so-called "paraffin dirt" of the Gulf Coast oil fields has been considered an indication of the possible presence of oil and gas, and not a few wells have been brought in solely on the basis of such evidence. In a sense, it may be empirically justified as evidence of the presence of oil or gas, though it cannot be said to be infallible. If the writer is correctly informed, its association with oil and gas was pointed out by Lee Hager some years ago, and while it is commonly mentioned by geologists and operators in conversation, no discussion seems to have found its way into print. The present interpretation is based on laboratory study rather than on field investigation, and is put forth with the hope of stimulating discussion which shall lead to more complete understanding. The term "paraffin dirt" has been applied to soils with a peculiar texture, which has been described as "curdy" or "rubbery." When moist, the material breaks much after the fashion of "green" cheese. It is rubbery under compression, but does not resemble rubber in tenacity or cohesion. When dry, the material ranges from hard clods to a horny mass of high tensile strength. The shrinkage in drying is very great, especially in the hornlike matter. The moist material ranges in color from dark brown in the specimens rich in organic matter to grayish in specimens containing more inorganic matter. All of the specimens studied were readily attacked by molds, which in some cases grew in great profusion on the samples. Samples exhibited a rather characteristic "swampy" or "mucky" odor when wet, and a characteristic odor of humic soils when moist. If the material is brought into suspension in water, very fine sand settles out and may be recovered by successive washing and decantation. The sand is almost entirely quartz, but contains occasional fragments of feldspar—more or less kaolinized and iron-stained. Practically all of the sand passes through a 100-mesh screen and the grains are extremely sharp —possibly below the limit of rounding. A flocculent mud, of clay and organic matter, remains in suspension for days. Some material is taken into solution in the water, imparting a slight tendency to froth when vigorously shaken. The results of partial analyses of four samples of "paraffin dirt," and, for comparison, one of a coastal plain soil are given in Table I.

Jan 1, 1920

By H. A. Bedworth

ALLOYS of copper and silicon have been known for one hundred years or more but the commercial development of this type of alloy has taken place during the past few years. In 1905, Sperry1 proposed the use of copper-silicon alloys for springs and other purposes for which copper-tin bronzes were used. Some attention was given to this proposal at the time but no one succeeded in producing a practical alloy containing more than a fraction of a per cent. of silicon. The equilibrium relations of the copper-silicon system were studied first by Rudolfi2 and later by Sanfourche3 and Corson.4 The constitution of the system has also been recently investigated by Matuyama,5 and in the laboratories of the American Brass Co. by Smith.6 Some of the physical properties of the copper-silicon alloys have been investigated by Norbury7 and by Geiss and Van Liempt.8 Summarizing the results of various investigators of, the constitution of copper-silicon alloys, the solubility reaches its maximum value, 6.7 per cent. silicon, between 721° and 782° C. At 852° C. the solubility is 5.25 per cent., while at 400° C. it is only 4.1 percent. silicon. The copper-silicon alloy begins to get so hard at about 3 per cent. silicon that it is difficult to manage. It was found by Jacobs that the addition of manganese to this alloy considerably improved the working

Jan 1, 1929

By E. D. Fields, R. W. Sayers, M. C. Tippett

The Duval Corp. porphyry copper deposits at Copper Canyon and Copper Basin, though widely separated, form an econornic unit requiring integrated exploitation. Contrasts in mineralization, host rocks, and mode of occurrence present unique mining and milling problems. Mixed oxide-sulfide ore is treated in extensive dump leaching facilities in both areas. Complex Cu-Au-Ag ore is treated in a 4000-tpd mill at Copper Canyon. In both areas, hypogene metallization occurs within large aureoles of metamoiphism and hydrothennal alteration related to quartz monzonite intrusions of mid-Tertiary age. Supergene processes fitrther altered the rocks and enriched the hypogene protore. At Copper Canyon, hypogene copper and iron sulfides with gold and silver occur in fractures, as partial replacement of favorable beds, and as disseminations in Paleozoic sedimentary rocks. The lower part of the Pennsylvanian Battle formation was a particularly favorable host. Metallization occurs to a lesser extent in quartz monzonite. Metal zoning is well-developed. The deposits at Copper Basin consist principally of supergene copper minerals in arenites of the Cambrian Harmony formation. Oxidation of hypogene copper and iron sulfides in tactite zones has formed at least two commercial deposits; intersections of fractures with favorable beds exerted important ore controls. Recently, the Copper Canyon and Copper Basin properties of Duval Corp. have been added to the list of porphyry copper mines in Nevada, marking the first new copper open pit in this state in 15 years. The properties are situated in the Battle Mountain

Jan 1, 1970

By F. Forscher

Pronounced porosity, decreasing with distance from the fracture surface, is found in the necked region of tensile specimens tested at room temperature or liquid nitrogen temperature. A hydrogen solution treatment followed by a quench prevents pore formation in tests at —196°C, but has little effect on tests made at room temperature. Reduction of area values at —196°C are strikingly improved by the same treatment, but show no improvement in room temperature tests. The experimental results support the hypothesis that strain-induced porosity results with hydride initially present or, in material containing less than 50 ppm H, with hydride precipitated by strain aging. ZIRCONIUM'S advent as an engineering material in nuclear reactor construction has brought forth many investigations concerned with the properties of this metal and its alloys. Some attention has been given to the ductility of the metal.1, 2 Particularly, the effect of hydrogen on the impact strength was noted," indicating a pronounced dependence of ductility on the hydrogen content and its distribution in the metal. Micro graphic:' and X-ray diffraction studies' have shown that a precipitated hydride phase causes embrittlement in zirconium,' which implies a distinctly different mechanism from that causing hydrogen embrittlement in steels."-' In the latter case, it is assumed that atomic hydrogen diffuses to rifts, where it forms molecular hydrogen under such internal pressures that it causes the rifts to enlarge, leading to fracture. Thermo-dynamic studies of the Zr-H system8, 9 also indicate that the internal pressure of molecular hydrogen would be too low to cause any damage to the zirconium at room temperature, and the formation of a zirconium hydride (d phase) is favored." It is noteworthy that this phase has a face-centered-cubic structure and nearly 18 pet larger molar volume than close-packed-hexagonal a-zlrconlum' Other features of the ductility of zirconium are the absence of a typical cup-cone failure upon tensile testing, a pronounced strain-induced porosity in the necked region of a tensile bar, Fig 1, and the associated spongy appearance of the fracture surface A tremendous improvement in ductility at liquid nitrogen temperature can be observed following a heat treatment that retains the commonly present quan- tities (10 to 50 ppm) of hydrogen in solution. Such tests show a typical cup-cone failure and the absence of strain-induced porosity, Fig. 2. The present paper reports results of an investigation into the causes of strain-induced porosity in zirconium. Room temperature tensile fractures of mild steel, aluminum, and titanium have also been examined for strain-induced porosity. In each case porosity could be detected, but the amount was orders of magnitude less than was found in zirconium. Of the three metals, titanium showed the strongest effect. Material, Specimens, and Preparation The greater part of this investigation was done on Westinghouse crystal bar zirconium, are-melted, forged, and hot-rolled. Chemical analyses of the hot-rolled plates are given in Table I, along with those of the Foote crystal bar zirconium used in this work. The specimens were machined from the hot-rolled plate (1550°F) of 1/2 in. thickness and subsequently heat-treated according to one of the treatments shown in Table IS. All specimens were machined round, the longitudinal axis in the rolling direction, with a gage

Jan 1, 1957

By A. E. Dwight, A. F. Berndt

Binary and ternary alloys of uranium with transition metals were prepared with U2X stoichiometry. The compounds U2Tc, U2Rh, U2Os, and U2lr were formed by peritectic or peritectoid transformations, and were shown to be isostructural with U2Ru. The lattice constants are presented. Miscibility relationships obtained from the study of ternary alloys are graphically summarized in terms of an area-of-stability plot. The compound U2Re is not isostructural with either U2Ru or U2Mo. A series of compounds with stoichiometry U2X has been prepared in which X is technetium, rhodium, rhenium, osmium, or iridium. The only other U2X compounds, for which X is related to the above transition metals by proximity in the periodic table, are U2Mo and U2Ru. The structure of U2Mo is the tetragonal C11b type (MoSi2 type)1 and U2Ru is monoclinic, with a new structure type.' This investigation was undertaken to determine if any of the above compounds are isostructural with either U2Ru or U2Mo and to find the range of occurrence of these phases. EXPERIMENTAL Alloys were prepared from stoichiometric amounts of electrolytic uranium (99.99 pet pure) and transition metals of 99.5 pet purity (98+ pet pure Tc), by arc melting on a water-cooled copper hearth under an Ar-He atmosphere. Weight losses were negligible. The buttons were homogenized at temperatures between 700o and 800°C (900°C for U2Tc) in evacuated capsules and air-cooled. The X-ray powder specimens were annealed briefly at the temperature of homogenization. Except in the case of the technetium alloy, metallographic examination was used to determine the number of phases present. The radiation hazard involved in handling technetium precluded the use of metallography to examine U2Tc. The temperature and mode of formation of the U2X phases were determined by heating the metallographic specimens to successively higher temperatures, until examination indicated the presence of chilled liquid or a peritectoid transformation. RESULTS The U2X compounds investigated were found to be formed under the following conditions: UzTc unknown U2Ru peritectic 897o ± 3°C U2Rh peritectoid 755o ± 5°C U2Re peritectoid3 below 750°C Uas peritectic4 920°C U2Ir peritectoid 775o ± 5oC Debye-Scherrer patterns for the above U2X phases were made with CuKa radiation (nickel filter). The similarities in the positions and intensities of the strongest lines in the front-reflection region strongly suggested that U2Tc, U2Ru, U2Rh, U2Os, and U21r are isostructural with only minor differences in the unit-cell dimensions. The known lattice constants and intensities of the Debye-Scherrer rings for U2RU2 were used as a guide in order to index the low-angle X-ray reflections of the U2TC, U2Rh, U2Os, and U2Ir powder patterns. Approximate lattice constants for these compounds were thus obtained and were used along with the intensities observed for U2Ru to index the strongest lines in the back-reflection regions. A sin2 2? correction term was included and the lattice constants were refined and standard deviations estimated by least squares. Comparison of observed and calculated values of Q(= 4 sin2?/?2) used in these calculations are given in Table I. In each case when the positions of lines could not be resolved on the films they were not measured. The final lattice constants, with their standard deviations, are given in Table 11, along with the unit-cell volume and X-ray density. The values of the atomic volume5 of the transition ele-

Jan 1, 1965

By F. E. Harris

It has been said that carbon is "ubiquitous" with reference to iron alloys. Certainly at temperatures where carbon and iron form the solid solution, austenite, it may be readily added to, or removed from, steel surfaces. Differences in concentration potential are the sole requirements for carbon flow. To measure the rate of carbon flow, a proportionality factor, D, is arbitrarily expressed in units of (length)2 X (time)-'. If the term used for carbon concentration is weight Pet C, as is customary, then a factor must be found, changing this term to One of weight Per unit volume when the diffusion coeficient, D, is used in flow formulae. The determination of D values for carbon is complicated since D varies with the concentration itself. The Matano method has often been employed for systems involving a variant D. This method expresses all evaluation of unsteady flow whereby D is given a relationship with the numerical value of C-x slopes. The author contends that this solution is incorrect, except when D is invariant. The primary purpose of this paper is to support this contention. Here diffusion is controlled under two conditions of flow. The first part deals with the steady state; the second part considers unsteady flow under definite restrictions. Beginning with the fundamental concept, the development is continued until equations for C-x curves are obtained. The solution is then subjected to experimental data. It is realized that a great amount of reliable data is required for a rigorous proof. KO such research is claimed. Instead an attempt is made to set forth the physical significance of the diffusion mechanism, and particularly to express the factors which influence the flow of carbon in austenite. Of equal significance is the implication that gaseous media may be employed with reasonable accuracy in making these determinations. The Steady State Diffusion of Carbon in Au~tenite The fundamental experiment defining diffusion in solid metals may be readily performed for carbon in gamma iron.' For this experiment a thin plate of medium carbon steel is chosen. The surfaces of this plate may be taken as two parallel planes which may be considered infinite for points well in the Center of the planes. These two planes are held at different concentrations of carbon at a constant temperature. This temperature, 1700°F for example, is one where the single phase: carbon in solution with gamma iron, exists. When these conditions are held for a sufficient time the concentration of carbon of the different points of the solid ment down towards its steady state value. At points well removed from the ends, the concentration will remain the Same along planes parallel to the surfaces of the plate.

Jan 1, 1948

By F. E. Harris

It has been said that carbon is "ubiquitous" with reference to iron alloys. Certainly at temperatures where carbon and iron form the solid solution, austenite, it may be readily added to, or removed from, steel surfaces. Differences in concentration potential are the sole requirements for carbon flow. To measure the rate of carbon flow, a proportionality factor, D, is arbitrarily expressed in units of (length)2 X (time)-'. If the term used for carbon concentration is weight Pet C, as is customary, then a factor must be found, changing this term to One of weight Per unit volume when the diffusion coeficient, D, is used in flow formulae. The determination of D values for carbon is complicated since D varies with the concentration itself. The Matano method has often been employed for systems involving a variant D. This method expresses all evaluation of unsteady flow whereby D is given a relationship with the numerical value of C-x slopes. The author contends that this solution is incorrect, except when D is invariant. The primary purpose of this paper is to support this contention. Here diffusion is controlled under two conditions of flow. The first part deals with the steady state; the second part considers unsteady flow under definite restrictions. Beginning with the fundamental concept, the development is continued until equations for C-x curves are obtained. The solution is then subjected to experimental data. It is realized that a great amount of reliable data is required for a rigorous proof. KO such research is claimed. Instead an attempt is made to set forth the physical significance of the diffusion mechanism, and particularly to express the factors which influence the flow of carbon in austenite. Of equal significance is the implication that gaseous media may be employed with reasonable accuracy in making these determinations. The Steady State Diffusion of Carbon in Au~tenite The fundamental experiment defining diffusion in solid metals may be readily performed for carbon in gamma iron.' For this experiment a thin plate of medium carbon steel is chosen. The surfaces of this plate may be taken as two parallel planes which may be considered infinite for points well in the Center of the planes. These two planes are held at different concentrations of carbon at a constant temperature. This temperature, 1700°F for example, is one where the single phase: carbon in solution with gamma iron, exists. When these conditions are held for a sufficient time the concentration of carbon of the different points of the solid ment down towards its steady state value. At points well removed from the ends, the concentration will remain the Same along planes parallel to the surfaces of the plate.

Jan 1, 1948

From the historical account of the coal industry set forth in the preceding pages the reader will have learned that coal is extremely widely spread throughout the United States, and in most places it has been easily found, that it has been remarkably easy to develop, and, where the deposits were available to streams on which it could be transported to markets, it was opened almost as soon as the country was settled. Such were the mines along the James, Susquehanna, Monongahela, Ohio, Kentucky, Cumberland and Big Muddy Rivers. In other localities where such easy means of transport were not convenient, the early production was confined to local use, or to places to which it could be hauled by wagons, but everywhere small mines were established almost as soon as the country was settled, and these increased both in number and size as the available markets grew. These early mines were nearly always opened by local people, and the industry was so far-flung that its growth attracted little or no attention excepting when a labor disturbance or a breakdown in transportation occurred. Had it been concentrated in a few places as most metal industries were, or as the petroleum industry was for many years after it started, it is probable that much better records of its progress would have been kept. When the canal era began, in the eighteen twenties, coal was at first not considered as a valuable source of freight revenue, and much surprise was expressed that the receipts of the Schuylkill Canal were very largely from coal after the first few years, as was the case of the Union Canal though not to such an extent. Even the early railroads to the coal fields did not realize the extent to which the products of mines would figure in their revenues, and it was many years before railroads were built practically solely for prospective coal traffic; indeed this did not happen until some years after the Civil War. Map 12 shows the extent of the canal system in the United States in its relation to the coal fields at the time of its maximum development. It will be seen that only the coal areas in Pennsylvania, Ohio, and to a very small extent in Indiana were able to ship by canal at all, and that only a very small portion of such fields could do so. Looking backward, it is hard to understand the great hopes entertained of canals by their pro-

Jan 1, 1942

By George G. Binder Jr., James W. Lacey, Arthur L. Draper

An experimental investigation of miscible fluid displacement has been made in linear porous media under highly adverse mobility ratio conditions. Various refined oils were displaced at field rates by liquid propane in both horizontal and vertical models 9 to 36 ft in length. In horizontal tests, mixed zones or transition zones form between the two liquids early in the displace-lents. Initially, the zones grow rapidly. III 2-in. diameter models, the mixed regions become nearly stable zones from 6- to 20-ft long. From then on these quasi-stable zones apparently grow only by molecular diffusion. The lenghts of the quasi-stable zones appear to be almost independent of the core material in which displacement;; are made and increase with increasing rates of injection and oil/solvent viscosity ratios. The lengths of the quasi-stable zones. measured in 2-in. diameter models at viscosity ratios and injection rates anticipated in the field indicate that essentially piston-like displacements of oil by solvent would occur. However, the mixed zone lengths increase markedly as the model diameter increases. In vertical displacements controlled by gravity drainage, only short trans-sition zones form. The entire lenghts of these zones can be accounted for by molecular diffusion. Therefore, in reservoirs having characteristics allowing a high degree of gravity drainage, nearly complete oil recovery should be attainable by miscible fluid displacement. INTRODUCTION The oil industry is faced with an ever increasing cost for finding new oil reservoirs. This, coupled with the fact that conventional methods of oil recovery usually leave from 1 to 3 bbl of oil in the ground for every barrel produced, has aroused considerable interest in developing more efficient methods. An integral part of the mechanism of many of these new methods of recovery is a miscible fluid displacement in which oil is displaced by a much less viscous materiai such as liquid propane. A numher of irlvestigators have explored the mechanics of miscible fluid displace-ment,'.2.1.'."." but in the experiments reported many of the important factors have been varied only over a limited range far removed from norma1 oilfield values. This paper presents the results of an experimental study of oil displacement by liquid propane at field rates from linear, natural-sandstone models of various sizes. Both horizontal and vertical flow tests were made. EXPERIMENTAL APPARATUS AND PROCEDURE Refined oils with viscosities varying over a wide range were displaced at several rates by liquid Propane from both horizontal and vertical flow systems. The behavior of the displacement was observed by propane-oil analyses of the effluent and, when possible, by differential pressure measurements along the cores. A schematic flow diagram of the apParatus used to conduct the experirents is shown in Fig. 1. The cores used in the tests were 9-ft lengths cut from natural consolidated sandstone and turned to the desired diameter. These were cast in steel tubing with a low melting point (160°F) alloy which expands on solidification. Flanges welded to the ends of the steel pipes permitted sealing the ends or butting one core to another. Pressure seals were maintained with O-rings. The cores were cleaned by flushing

By F. H. Allen, R. P. Roe

The performance history of a volumetric gas condensate reservoir is presented. Curves depict the pressure-production relation and illustrate the phace behavior of the reservoir fluid. This performance is compared to calculated performance. This Bacon Lime Reservoir was discovered in 1941 and has been produced to field separators and gas sales. Reservoir performance has been observed by periodic bottom hole pressure sur. veys and companion sample analysis of well effluents, in addition to gas and condensate production data. , The pressure-production history demonstrates that the reservoir has produced under volumetric control. The "retrograde" behavior of the reservoir fluid is illustrated by decreasing butanes-plus content of the well effluent, followed by revaporization as the reservoir pressure approaches abandonment. Calculated performance predictions are compared to actual performance and some discussion offered on apparent discrepancies. INTRODUCTION Since the late 1930's, many gas condensate reservoirs have been developed, the retrograde theory of phase behavior has been generally accepted, and a number of cycling programs have been initiated. Numerous technical papers have since appeared in the literature dealing with the theory and application of cycling the gas condensate reservoirs. Some cycling operations have now advanced to a stage where it is possible to determine performance characteristics to a fair degree of accuracy. Field performance data for gas condensate reservoirs operated by pressure depletion have not been so extensively reported in the literature, although their probable behavior has been discussed in explanation of the retrograde theory. It is the purpose of this paper to compare calculated theoretical reservoir performance with field observations and well stream analyze; which have been obtained throughout the practical producing life of a small volumetric gas condensate reservoir. The reservoir under study is the Bacon Lime Zone of a field located in East Texas. The Bacon Lime occurs in the Lower Glen Rose Formation of Cretaceous Age. This Bacon Lime Reservoir is encountered at an average depth of 7600 ft (7203 ft subsea elevation) and comprises approximately 3100 acres located on a structural high with 80 ft of productive closure. The producing formation consists of approximately 50 ft of dense crystalline fossiliferous dolomite of generally low permeability with typical wide variation in both permeability and porosity, the more permeable stringers measuring 30 to 40 millidarcys. The average porosity is extimated to be 10 per cent with a connate water saturation of approximately 30 per cent of the pore space. The reservoir temperature was found to be 220°F and the original pressure was 3691 psia at -7200 ft elevation. The re ervoir was discovered in November, 1.941, and is now essentially depleted, Throughout most of its productive life, from the standpoint of cumulative withdrawals, the reservoir has been produced by five wells. During its latter stages of depletion, 16 wells were completed in the Bacon Lime.

Jan 1, 1950

By A. R. Kinkel

THE Shasta copper-zinc district of northern California lies in the foothills of the Klamath Mountains at the northern end of the Sacramento Valley. It contains two main areas of base-metal ore deposits, the East Shasta and West Shasta districts shown in Fig. 1. The East Shasta includes the area from the Afterthought mine, near the settlement of Ingot on U. S. highway 299 East, to the Bully Hill mine, on the north side of the Pit River, 9 miles to the northwest. The West Shasta, a well-defined northeast-trending district about 8 miles long and 2 miles wide, west of the Sacramento River, Fig. 2, is the western part of the ore-bearing area formerly known as the Shasta copper belt. Referred to in the older writings as a copper arc, this belt was thought to form a crescent extending entirely around the head of the Sacramento Valley, the convex side to the north. Recent studies by the U. S. Geological Survey in cooperation with the California State Division of Mines show that there are two districts, one at each end of the so-called copper arc, which are distinct in geologic structure and ore occurrences, and that there is only sporadic and unconnected copper mineralization between them. Ore deposits of the two districts are similar in mineralogy, that is, they are largely massive pyritic ores containing copper and zinc with minor amounts of gold and silver, but the structure and structural control of ore deposition are different. The ores of the East Shasta district are replacements of steeply dipping shear zones in Triassic rhyolite and shale, whereas those of the West Shasta district are replacements of gently dipping rhyolite of Middle Devonian age and are essentially flat-lying. Thus there is marked lateral control of orebodies by shear zones in the East Shasta district and equally marked vertical control of orebodies by the stratigraphy in the West Shasta district. Geologic Setting The Paleozoic rocks of the West Shasta district range in age from Middle Devonian (?) to Missis-sippian. The oldest formation exposed is the Copley greenstone, probably Middle Devonian. It is composed of volcanic flows, volcanic breccias, and tuffs, all of mafic composition, but contains minor amounts of shale and rhyolitic tuff. Largely submarine in origin, it rests upon a base of older marine sediments, as shown diagrammatically in Fig. 3. The lower part of the formation is made up principally of flows, many of which are ellipsoidal, and the upper part contains most of the pyroclastic material. The formation is at least 3700 ft thick. The Balaklala rhyolite overlying the Copley greenstone is made up of many rhyolitic flows and beds

Jan 1, 1956

By Elmer R. Kaiser

COMBUSTION of coal and transfer of heat from flames and gases to boiler surfaces continue to be of great interest to engineers here and abroad. Numerous investigations have been in progress to improve furnace and boiler performance and economy. The importance of better understanding of the processes and opportunities for improvement is apparent when it is remembered that heat from at least 500 million tons of coal a year the world over is being transferred to boiler water at efficiencies ranging mostly between 50 and 90 pct. Even slight gains in efficiency, economy, and labor saving become very significant when multiplied by the enormous quantity of fuel consumed. Also the competitive position of the large coal, oil, and gas industries in satisfying the fuel consumers is greatly affected by the achievements made through technical progress with each fuel. This paper is part of a continuing activity of Bituminous Coal Research, Inc., to extend the knowledge of coal utilization for steam generation and to seek promising directions for future research and development in cooperation with others. Particularly in the latter regard, numerous interviews were held during the last three years to seek the experience and advice of boiler and combustion-equipment manufacturers, electric-utility executives, and fuel engineers. A wealth of published information was also reviewed, which together with the interviews pointed to the advisability of further work on ash and sulphur control. For the present purpose a number of factors important to efficient heat liberation and recovery have been grouped as follows: 1—combustion, temperatures, and rates of heat liberation; 2—radiation, convection, and furnace and boiler configuration; 3—sponge ash, slag, and hard-bonded deposits; 4— low-temperature deposits and corrosion (cooling flue gas below dew point and air-pollution control); 5—the limitations of coal cleaning and boiler size and cost as related to fuel characteristics; 6—future possibilities and conclusions. The development of combustion apparatus for power boilers is progressing at a lively pace. There has been no letup in improvements in design of pulverized-coal-fired boilers, and there is a strong trend at present toward improving dry-bottom units. Spreader stokers with overfire jets and dust collectors as standard equipment are gaining favor. Less than 10 years in commercial use, cyclone burners are going into numerous installations here' and abroad.' Underfeed and traveling-grate stokers have long since been developed for heavy-duty operation, yet new developments in overfire jets and humidification of air blast have improved their performance. A water-cooled vibrating-grate stoker of German origin is being introduced into the United States and Canada." The primary objectives of an ideal coal combustion device are: capacity to burn the variety and sizes of coals likely to be economically available during the life of the unit; capacity to burn the coals automatically for a wide load range and rapid load fluctuations and to burn the coals completely to CO2, H2O, and SO2, which means without smoke and cinders, or carbon in the refuse; capacity to control and discharge all the ash in final granular form without ash adhesion to walls or tubes, and without flue dust; minimum furnace volume; minimum labor and maintenance; low initial and operating cost. Regardless of the method of burning, the gaseous products of coal combustion are N2, CO2, O2, H20, and SO?. By way of illustration, the coal analyses in Table I is assumed from an installation described by E. McCarthy.' When coal is burned with 20 pct excess air (theoretical air, 9.23 lb per lb of coal), the quantities of combustion gas shown in Table II are produced. In addition, the gases carry particles of fly ash, unconsumed cinders, soot particles, and small but significant amounts of vaporized oxides and sulphates of sodium, potassium, lithium, phosghorous, iron, and other metals. In recent years, germanium, one of the rare metals found in coal, has been shown to oxidize and vaporize at combustion temperatures and to be concentrated by reconden-sation at lower temperatures." Pulverized coal and cyclone flames" have peak temperatures of 3000' to 3500°F. Temperatures in fuel beds of large underfeed stokers reach maxima of 3000°F, sufficient to fuse almost any ash and to volatilize some of it. These peak temperatures are above the optimum necessary for rapid combustion, but they hasten heat transfer for ignition as well as boiler heat absorption. Furnace and gas temperatures increase with combustion air preheat. Low excess air has the same effect. Fine coal pulverization and highly turbulent combustion shorten the distance for fuel burnout, increase flame temperature, and speed up heat transfer. Rates of combustion of pulverized coal exceeding 200,000 Btu per cu ft per hr have been demonstrated in atmospheric gas-turbine combusters,

Jan 1, 1955

By Joseph E. Pogue

In 1920, 531 million barrels of crude petroleum were coi~sumed in the United States. As imposing as this figure is, the fact that the domestic consumption of crude petroleum has increased at an average rate of 10 per cent. a year for the past decade is more striking. Will this rate of increase in demand continue? If so, the year 1930 will call for 1260 million barrels of petroleum—a staggering volume. On the other hand, may we expect the demand for petroleum to grow as rapidly as it did when the automotive industry was having its most phenomenal expansion? If not, to what extent will the growth of oil requirements decrease? When and to what degree will the petroleum industry become affected by the economic law of diminishing returns? Obviously, this matter requires careful analysis, especially as both national and industrial planning must be predicated upon present estimates of the requirements of the future. The purpose of this paper, accordingly, is to project, as closely as present limitations of knowledge permit, the course of the demand for petroleum in the United States over the next ten years. At first, the problem of estimating the future of a demand as complex as that for petroleum might appear insoluble. Fortunately, hon~ever, therc are several scientific methods of approaching the problem, centering around a study of rates of industrial growth, which lend considerable hope that the requirements of the immediate future in this field may be approximated with sufficient closeness to have practical value as a basis of action. Growth oF Petroleum Demand The demand for crude petroleum is the resultant of the demands for the products made jointly from this substance—gasoline, kerosene, gas and fuel oil, and lubricating oils. The demands for these have grown at

Jan 1, 1923

By Joseph E. Pogue

In 1920, 531 million barrels of crude petroleum were coi~sumed in the United States. As imposing as this figure is, the fact that the domestic consumption of crude petroleum has increased at an average rate of 10 per cent. a year for the past decade is more striking. Will this rate of increase in demand continue? If so, the year 1930 will call for 1260 million barrels of petroleum—a staggering volume. On the other hand, may we expect the demand for petroleum to grow as rapidly as it did when the automotive industry was having its most phenomenal expansion? If not, to what extent will the growth of oil requirements decrease? When and to what degree will the petroleum industry become affected by the economic law of diminishing returns? Obviously, this matter requires careful analysis, especially as both national and industrial planning must be predicated upon present estimates of the requirements of the future. The purpose of this paper, accordingly, is to project, as closely as present limitations of knowledge permit, the course of the demand for petroleum in the United States over the next ten years. At first, the problem of estimating the future of a demand as complex as that for petroleum might appear insoluble. Fortunately, hon~ever, therc are several scientific methods of approaching the problem, centering around a study of rates of industrial growth, which lend considerable hope that the requirements of the immediate future in this field may be approximated with sufficient closeness to have practical value as a basis of action. Growth oF Petroleum Demand The demand for crude petroleum is the resultant of the demands for the products made jointly from this substance—gasoline, kerosene, gas and fuel oil, and lubricating oils. The demands for these have grown at

Jan 1, 1923