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By W. O. Philbrook, A. E. El-Mehairy

The reduction by hydrogen of individual particles of dense hematite implanted in beds of inert spheres is controlled by single-particle kinetics. No evidence of reagent starvation was found down to low flow rates established by pressure gradients as low as 0.01 in. H2O per- in. of depth in beds of spheres as small as 3/16 in. diam. The optimum size for most rapid reduction of beds of homogeneous ores results from the effect on reducing potential of the gas of competing factors of supply and consumption. A recent publication1 presented the results of a study of the rate of reduction of iron ore in a fixed bed by hydrogen introduced at constant pressure differential. Under these conditions the reagent flow rate varied directly with the bed permeability, which was a function of particle size and shape and bed voidage, and inversely with the temperature-dependent viscosity of the gas. The present note adds data from supplementary experiments designed to reveal whether or not any partial reagent starvation arising from a flow-dependent transport resistance in the gas phase might have been operative. Kinetic studies were made of the reduction of individual spheres of iron oxide inserted into beds of inert spheres, so that the reagent flow rate and aerodynamic conditions were again determined by bed characteristics and temperature. The experimental techniques and apparatus were similar to those previously described.' The synthetic iron ore spheres were wet-rolled by hand from powdered, reagent-grade* Fe2O3 and subsequently dried and then fired in air at 1250°C. The indurated pellets has almost no porosity as indicated by their specific gravity of 5.10. The beds were made of dense alumina spheres, closely sized to the same dimension as the iron oxide spheres, in the following diameters: 3/16, 1/4, 5/16, and 3/8 in. Each bed was hand-packed of particles of a single size to a controlled voidage of 0.32 and depth of 3 in. within a capsule having an internal diameter at least 10 times the particle diameter. A few weighed iron oxide spheres were individually planted in the central plane of the bed of inert spheres at points away from the wall. Reduction was carried out at atmospheric pressure by purified hydrogen at 670°, 800°, and 985°c. The reagent was supplied at precisely controlled pressure differentials of 0.01, 0.02, and 0.03 in. of water per in. of bed depth. This gave a range of flow rates similar to that used in the study of beds of ore and comparable with blast-furnace practice in terms of mols of reducing gas per hr per sq ft of cross-section. Viscous flow prevailed in all beds under the experimental conditions of this study. The reduced particles were checked for loss in weight and then sectioned for metallographic examination. Occasional particles were found to have contained minute internal cracks that interfered with the concentricity of the reduction interfaces, and data for such particles were rejected. An experimental rate constant for the reduction of the imbedded Fe2O3 spheres was calculated on the assumption that the rate was proportional to the metal-oxide interface area by an equation that has been found by McKewan2 to describe the reduction of single spheres

Jan 1, 1962

By Paul M. Musgrove, Larry S. Diaz

Recent tests conducted at Inspiration Consolidated Copper Co. examined some aspects of the value of a continuous measurement of particle size to the operation and control of a mill grinding circuit. Inspiration's control objectives and kinds of control systems developed in recent years to attain these objectives are outlined. A description is given of the arrangement of the test circuit at Inspiration and also of the systems used to measure particle size of the cyclone overflow product in these tests. Use of on-line size measurement for the analysis and improvement of grinding circuit performance is illustrated by relating how two important relationships were detected. Finally, the performance of a particle-size-based control system is described, including preliminary conclusions as to increased productivity.

Jan 1, 1974

By Leonid V. Azároff, H. N. Murty

In the course of investigating the soft X-ray absorption spectra of Ni-A1 alloys, Das and ~zfiroff' observed an anomalous brittleness in solid solutions containing 3 to 5 at. pct Al. The brittle alloys also had anomalously larger lattice constants' and the fine structure at the nickel K edge of an alloy containing 3.96 at. pct A1 unexpectedly resembled that of NiA1 more closely than that of a solid solution containing 5.51 at. pct Al. This led them to suggest the possibility that short-range ordering was produced during the homogenization anneal to which each specimen was subjected, similar to that observed in dilute solutions of vanadium and of chromium in nickel: as the principal cause of embrittlement. It was decided to repeat the above measurements on several alloys in this composition range in order to test the above hypothesis and to establish the effect of heat treatment on the alloys' properties. Three solid solutions in this range were prepared containing, respectively, 3.16, 4.00, and 4.54 at. pct Al, in addition to alloys containing 6 and 9 pct. All samples were annealed in vacuum at 1800°F for 100 hr and then furnace-cooled to room temperature, as in the original study. The lattice constants of these alloys are shown by open circles in Fig. 1 and can be seen to fit quite closely the curve established by the previously measured values, indicated by solid circles. (The experimental errors are of the order of the size of the circles, +o.oo~R.) The three alloys containing 3 to 5 at. pct A1 were found to be quite brittle, as previously reported. In order to test the possibility of ordering, these three solid solutions were again heated to 1800°F and, following a few hours at that temperature, were quenched directly to room temperature. All three alloys lost their brittleness. In order to verify the proposed ordering hypothesis, it was decided to subject each sample to several cycles of quenching and annealing (disordering and ordering). After some experimentation, it was established that reproducible results could be obtained by anneal-

Jan 1, 1968

By Henry B. Smith, S. Paul Lindau

ThREe years ago it was decided by the management to granulate the matte that is produced in the smelter of the St. Joseph Lead Co. at Hereulaneum, Mo., thereby doing away with a large amount of labor in handling the matte and in subsequent crushing. On Mar. 1, 1915, the granulator was put in operation and up to Jan. 1, 1916, 18,735 tons had been granulated. The four blast furnaces have a daily output of about 280 tons of pig lead and 100 tons of matte assaying about 11.0 per cent. Pb. It is expected that projected improvements in roasting methods will eliminate more sulphur from the charge, and cut down the matte-fall to about one-half of the present figure. The blast furnaces are tapped into movable forehearths or settlers, 6 ft. by 4 ft. by 22 in., the slag overflowing into 27-cu. ft. slag cars which are hauled to the dump by electric locomotives. Previous to the adoption of granulation, the matte was tapped from the forehearths into small slag pots which were dumped after cooling. The matte cakes were broken with sledges, and transported to the crushing plant for fine crushing and screening. Here the matte was reduced to 1/4-in. size before being fed to the roaster bins. A Wedge and a Holthoff mechanical furnace are used for preroasting before sintering on the Dwight and Lloyd machines. The matte is returned to the furnaces as an iron flux until the gradually accumulating copper content reaches about 7 per cent., after which it is put aside to be concentrated in a small copper blast furnace, the resultant high-grade matte being sold. When the matte does not settle readily from the slag, two settling devices are often used, the second one being a large catch-pot, which gathers any matte that may overflow from the forehearth, the slag then overflowing from the catch-pot into the slag cars. When full of matte, the catch-pot is removed, allowed to cool, and the contents broken and crushed. a With the present plan of granulating, the matte is tapped into 6-cu. ft. iron ladles. These are transported to the granulating plant by a 5-ton

Jan 1, 1917

By Edward B. Hughes, Frank G. Norris

OXIDATION is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the most recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a, compound such as C02-or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct, method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is introduced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steelmaking," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath. A recent article12 reviewing the current

Jan 1, 1948

By J. Chipman, J. C. Fulton

Reduction of Si from slag to carbon-saturated iron is a very slow reaction. The rate is nearly independent of stirring but is accelerated markedly by increased temperature. In a slag containing 45 pct SiO2, 38 pct CaO, 17 pct Al2O3, the energy of activation is approximately 130 kcal. AT temperatures of 1450" to 1600°C occurring in the hearth of the iron blast furnace, chemical reactions are normally expected to proceed with great rapidity. Many of the reactions of iron making are indeed quite rapid and attain a condition corresponding roughly to a state of equilibrium before metal and slag are tapped from the furnace. The one conspicuous exception is the reaction by which carbon in the coke or metal reacts with silica in the slag to deliver silicon to the metal. From the practical viewpoint the slowness of this reaction is indeed fortunate, for if it were fast enough to reach equilibrium during the time of contact, it would be difficult to produce pig iron of the desired low silicon content. The one other reaction which under certain circumstances can also be very slow is the transfer of sulfur from blast-furnace metal to slag. In their laboratory exeriments on this reaction, Hatch and Chipman found that at least 5 hr were required for the attainment of equilibrium in a small crucible and that the reaction was not accelerated by increasing the rate of stirring. Subsequently it was shown2 that the presence of a reducible oxide MnO greatly inhibited sulfur removal, and finally that SiO2 itself3 under some conditions has sufficient oxidizing Dower to interfere with sulfur transfer. The kinetics of sulfur removal are now rather well understood,4 and it has been shown3,5 that when the silicon content of the metal is high enough to prevent reduction of SiO,, the desulfurizing process is rapid. Thus the observations of slow removal of sulfur are associated with the coincident slow reduction of SiO2, a process which transfers both silicon and oxygen to the metal phase. It is, of course, the oxygen which interferes with sulfur removal. An explanation of the slowness of the silica reduction reaction has not been obtained. The sulfur transfer process has been shown by the authors5 to be at least partially transport-controlled in the absence of interference by silica. Under the experimental conditions. 99 pct of the total transfer at 1600" was accomplished within an hour. Under similar conditions the reduction of silica may not proceed half-way to equilibrium6 in 8 hr. It is scarcely imaginable that silica reduction could be transport-controlled when the slag contains 44 pct SiO2 and the metal about 1.4 pct C. The experiments reported here show definitely that it is controlled by a slow step or steps in the chemical reaction. One might expect to find such a slow step in the breaking of SiO bonds or in the slow removal of oxygen by carbon at the slag-metal or metal-crucible interface or by bubble formation. EXPERIMENTAL PROCEDURE The experimental procedure used in this investigation was similar to that used in the study of the kinetics of desulfurization.5 A sketch of the graphite crucible and stirrer used in the current work is shown in Fig. 1. The quantity of metal and slag used was adjusted so that the slag-metal interface was located between the top and bottom blades on the stirrer; the top of the slag layer was above the top blade. The stirrer shaft was hollow down to the metal level and served as thermocouple well or optical pyrometer target. Stirring speeds of 0 to 500 rpm were used. A carbon monoxide atmosphere was maintained in the furnace by flushing the gas over the slag surface, except in run No. 220 when it was bubbled

Jan 1, 1960

By W. J. Hillenbrand

The soda-ash method for eliminating arsenic from a molten copper bath has been described previously in some detail.' Briefly, the process consists in blowing powdered sodium carbonate under the surface of the partially oxidized melt and in removing the slag formed, which will contain a certain proportion of the arsenic formerly in the bath. Sodium carbonate melts readily at the temperature of molten copper, and when molten it dissolves arsenic oxide rather rapidly. In the process, sodium arsenate is formed which is removed along with the excess of molten soda ash. In order that arsenic may be eliminated in this way, it must first be oxidized to the pentavalent condition. This, however, is easily accomplished by blowing air into the molten copper until a fair excess of cuprous oxide is present. The manner in which soda ash is introduced into the furnace has a considerable effect upon the efficiency of the process. In the earliest attempts at arsenic removal, soda ash—often in combination with slaked lime, for sodium carbonate is not the only solvent that will remove arsenic—was thrown upon the surface of the bath, was allowed to melt, and was removed after it had dissolved a sufficient amount of arsenic. At present powdered soda ash is generally blown in under the surface of the melt with the aid of compressed air. Melting immediately as it comes into contact with the molten copper, it can react with considerably more of the bath than by the former method, and thus can remove arsenic more rapidly and more completely. Since the resulting slag is removed at once, its very destructive effect upon the furnace refractories is minimized. The effectiveness of the soda-ash method may be gathered from the results of the following test. A 900-lb. charge of copper was melted in a small, oil-fired reverberatory furnace, and sufficient metallic arsenic was added to the bath to bring the concentration of that element to about 0.5 per cent. Air was blown into the melt until its oxygen content was just under 1 per cent by weight. The bath was then sampled and soda ash was blown in under the surface in 5-lb. batches. After each addition

Jan 1, 1934

By Alfred H. Bell

Drilling activity in the eastern interior coal basin, which includes Illinois, southwestern Indiana and western Kentucky, decreased greatly in 1931. Only 521 wells were drilled as compared with 1438 in 1930.' The decline in oil production (Fig. 1) was due partly to the failure of new production to make up for the natural decline of the old wells and partly to artificial curtailment of production to meet a decreased demand. During the year prices trended sharply downward until July, after which they made a partial recovery (Fig. 2). The average price of Illinois crude, which is the same as that for southwestern Indiana, was $0.852 per barrel in 1931 as compared with $1.616 in 1930, or slightly more than one-half. The cost of drilling has declined only slightly. The 25 per cent curtailment of production which was adopted by agreement of the southeastern Illinois operators on Sept. 1, 1930, ended on June 3, 1931. It was effective for five months in 1931 as compared with four months in 1930. The outlook for 1932 is for drilling activity in the whole area to continue at about the same rate or to decrease somewhat unless it is stimulated by a substantial rise in crude oil prices or by the discovery of extensive new productive territory. Discoveries of new productive areas and new sands during the year were few. A new gas area was discovered early in the year in Busseron township, Knox County, Indiana, in which the producing sand is in the Pennsylvanian at depths of 630 to 730 ft. The wells had a total initial open-flow capacity of 7 or 8 million cubic feet per day but are shut in for lack of marketing facilities. An exceptionally large gas well which was drilled in Gibson County between Oakland City and Francisco reached a total depth of 1490 ft. and produced from the Brown sand of Chester age. The initial open-flow capacity was reported as 13 million cubic feet per day. In western Kentucky a number of extensions to oil and gas-producing areas are reported. The most active drilling campaign was in Hart County, where 124 wells were drilled, most of them in the

Jan 1, 1932

By C. T. Butler, W. W. Kay, R. D. Boddorff, R. L Ash

DRILLING and blasting in anthracite open-pit mines is a continuous problem to contractors and explosive engineers because of the diverse conditions caused by the nature of the geological formations, the extensive mining of the portions of coal beds near the surface, and the proximity of many strip pits to populated areas. Pennsylvania anthracite occurs in four separate long and narrow fields totaling only 480 sq miles. The coal measures are rock strata and coal beds that are considerably folded and faulted. The crests of the anticlines are eroded extensively. The beds outcrop on the mountain sides and dip under the valleys. At first only the upper portions of the syn-clines could be stripped. Now stripping to increasingly greater depths is economically possible, as is indicated by the fact that the proportion of freshly mined anthracite produced by strip mining has increased from 3.7 pct of the total tonnage in 1930 to 29.6 pct in 1950. Much of the rock overlying the deeper beds now being stripped is so extensively broken that considerable difficulty is experienced in drilling satisfactory blast holes and in using explosives in such manner as to insure a uniformly broken material easily removed by the excavating machinery. Such breaking of rock strata has occurred because the bed now being stripped has been mined extensively in former years by underground methods, and tops of gangways and chambers have subsequently failed. Draglines are used to uncover coal where the overburden can be moved with little or no re-handling. These machines range in size from those having a 2 cu yd capacity bucket on a 60-ft boom to those handling a 25 cu yd bucket on a 200-ft boom. Draglines are also used to strip to the bottom of the coal basins if the depth and the distance between the crops are not too great. For this type of operation blast holes are drilled full depth to the bed. These holes are commonly 30 to 90 ft deep; however, in exceptional cases, holes may be as shallow as 12 ft or as deep as 130 ft. Drilling is normally done for blasts of 12,000 to 60,000 cu yd of overburden, 30,000 cu yd being considered an average blast if vibration is not the controlling factor. Where the stripping of wide basins or the exposure of a moderately pitching vein makes the use of draglines impractical, dipper front shovels equipped with 4 to 6 cu yd buckets load into trucks. Overburden is removed in benches of 25 to 30 ft with blast holes drilled 4 or 5 ft deeper than the planned floor of the bench. For shovels under 5 cu yd bucket capacity the volume blasted varies from 8000 to 12,000 cu yd, whereas a volume of 30,000 to 50,000 cu yd of overburden is frequently blasted at one time for the larger shovels where vibration is not an important factor. During the past decade the churn drill, generally the Model 42-T Bucyrus-Erie blast hole drill equipped for drilling 9-in. diam holes, has become the most common blast hole drilling machine. Electricity powers half the churn drills in use and is preferred on the large strippings where electric shovels are operated and the working area is concentrated. On these operations the cost of additional electricity for the drills is less than the cost of fuel to operate diesel units because of the existing large demand load of the excavating equipment. Moreover, electric motors start more easily in cold weather and generally are less expensive to maintain. Diesel driven units are employed where a higher degree of mobility is required. The average drilling speed is 8 ft per hr, although in softer rocks a rate of 15 ft per hr is attained. Where rock is hard and strata is badly broken, drill speeds may be less than 2 ft per hr. Low drilling production results under these circumstances when loose material falling from the upper portion of the drill holes causes drill stems to be jammed. Rock formations vary so greatly in the region that a 9-in. diam churn drill bit may become dull after drilling only 2 ft or may drill satisfactorily for 56 ft; however, an average of 35 ft is usual in sandstone of medium hardness. Dull bits are hoisted to flat bed trucks by the sand line of the drill and are usually sharpened in the contractor's bit shop adjacent to the job. Care is generally taken to cover the thread end of the bit with a cap. To facilitate handling of bits around the drill, a heavy thread protector having an eye top is becoming more popular than the flat-top rubber or metal cap furnished with new bits. The 9-in. diam blast holes for a 25 to 30 ft bench are normally on 18x18 ft to 20x20 ft spacings, depending on the character of the overburden, although in broken ground 15x18 ft centers may be used to obtain better breakage and a more even bottom for the bench. The patterns of holes for shots

Jan 1, 1953

By R. D. Boddorff, R. L. Ash, C. T. Butler, W. W. Kay

DRILLING and blasting in anthracite open-pit mines is a continuous problem to contractors and explosive engineers because of the diverse conditions caused by the nature of the geological formations, the extensive mining of the portions of coal beds near the surface, and the proximity of many strip pits to populated areas. Pennsylvania anthracite occurs in four separate long and narrow fields totaling only 480 sq miles. The coal measures are rock strata and coal beds that are considerably folded and faulted. The crests of the anticlines are eroded extensively. The beds outcrop on the mountain sides and dip under the valleys. At first only the upper portions of the syn-clines could be stripped. Now stripping to increasingly greater depths is economically possible, as is indicated by the fact that the proportion of freshly mined anthracite produced by strip mining has increased from 3.7 pct of the total tonnage in 1930 to 29.6 pct in 1950. Much of the rock overlying the deeper beds now being stripped is so extensively broken that considerable difficulty is experienced in drilling satisfactory blast holes and in using explosives in such manner as to insure a uniformly broken material easily removed by the excavating machinery. Such breaking of rock strata has occurred because the bed now being stripped has been mined extensively in former years by underground methods, and tops of gangways and chambers have subsequently failed. Draglines are used to uncover coal where the overburden can be moved with little or no re-handling. These machines range in size from those having a 2 cu yd capacity bucket on a 60-ft boom to those handling a 25 cu yd bucket on a 200-ft boom. Draglines are also used to strip to the bottom of the coal basins if the depth and the distance between the crops are not too great. For this type of operation blast holes are drilled full depth to the bed. These holes are commonly 30 to 90 ft deep; however, in exceptional cases, holes may be as shallow as 12 ft or as deep as 130 ft. Drilling is normally done for blasts of 12,000 to 60,000 cu yd of overburden, 30,000 cu yd being considered an average blast if vibration is not the controlling factor. Where the stripping of wide basins or the exposure of a moderately pitching vein makes the use of draglines impractical, dipper front shovels equipped with 4 to 6 cu yd buckets load into trucks. Overburden is removed in benches of 25 to 30 ft with blast holes drilled 4 or 5 ft deeper than the planned floor of the bench. For shovels under 5 cu yd bucket capacity the volume blasted varies from 8000 to 12,000 cu yd, whereas a volume of 30,000 to 50,000 cu yd of overburden is frequently blasted at one time for the larger shovels where vibration is not an important factor. During the past decade the churn drill, generally the Model 42-T Bucyrus-Erie blast hole drill equipped for drilling 9-in. diam holes, has become the most common blast hole drilling machine. Electricity powers half the churn drills in use and is preferred on the large strippings where electric shovels are operated and the working area is concentrated. On these operations the cost of additional electricity for the drills is less than the cost of fuel to operate diesel units because of the existing large demand load of the excavating equipment. Moreover, electric motors start more easily in cold weather and generally are less expensive to maintain. Diesel driven units are employed where a higher degree of mobility is required. The average drilling speed is 8 ft per hr, although in softer rocks a rate of 15 ft per hr is attained. Where rock is hard and strata is badly broken, drill speeds may be less than 2 ft per hr. Low drilling production results under these circumstances when loose material falling from the upper portion of the drill holes causes drill stems to be jammed. Rock formations vary so greatly in the region that a 9-in. diam churn drill bit may become dull after drilling only 2 ft or may drill satisfactorily for 56 ft; however, an average of 35 ft is usual in sandstone of medium hardness. Dull bits are hoisted to flat bed trucks by the sand line of the drill and are usually sharpened in the contractor's bit shop adjacent to the job. Care is generally taken to cover the thread end of the bit with a cap. To facilitate handling of bits around the drill, a heavy thread protector having an eye top is becoming more popular than the flat-top rubber or metal cap furnished with new bits. The 9-in. diam blast holes for a 25 to 30 ft bench are normally on 18x18 ft to 20x20 ft spacings, depending on the character of the overburden, although in broken ground 15x18 ft centers may be used to obtain better breakage and a more even bottom for the bench. The patterns of holes for shots

Jan 1, 1953

By Robert B. Smith

The South Texas Mineral Trend is now estimated to contain uranium reserves of 150 million pounds U308 . Within the past year, an estimated 10 million pounds U308 have been added to this gross reserve. It is probable that a similar amount has been identified in previously unknown orebodies that, as yet, have not been delimited or announced. Exploration that was limited in the past to a narrow band containing only the known trend has now expanded into older sediments updip and into younger units towards the coast. Uranium host formations are also now being explored at a considerable depth and distance eastward from known deposits. Only about 30 percent of the potential uranium host rocks in South Texas have been adequately explored. Geology The South Texas uranium deposits are confined mainly to sediments of the Tertiary system. Reserves are divided almost equally between the Whitsett Formation of the Jackson Group, the Catahoula Formation, and the Oakville Formation. A minor amount of the reserves occurs in sands of the Goliad Formation which may be either in the Tertiary or Quaternary Epoch. Figure 1 is a geologic column of the South Texas uranium host formations. These producing formations are marked with a mine symbol but there are also several prospect symbols that denote potentially favorable uranium host formations both younger and older from the producing formations. It is generally accepted by most workers in South Texas that the source for the uranium is the volcanic ash that is abundant within several of the formations. Likewise, the required reductant is considered to be hydrogen sulfide gas, derived from deeper seated hydrocarbon accumulations, that emanate upward along fault zones into favorable host-rock sand units. Within this basic framework of source, host, structure and hydrocarbons is where most of the reserves have been discovered and where most of the current exploration is either concentrating or expanding. Structure in South Texas is predominantly faults. Swarms of faults exist in zones paralleling the coast and running from the Rio Grande to the Sabine River. These faults are usually growth faults with the down-dropped block on the coastward side. Displacement may range from a few feet to a few hundred feet. Dips are near vertical in the younger rocks at the surface but become flatter as the fault cuts older beds in the subsurface. A map of the oil and gas fields in South Texas indicates a correlation between these fault swarms and accumulations of hydrocarbons. It is not coincidental that the known uranium trends closely follow the hydrocarbon accumulations and the faults swarms, all of which supports the theory of uranium concentration by groundwater movement through volcanic ash-rich beds into favorable host rocks impregnated with reducing hydrogen sulfide gases that migrate upward along fault planes from hydrocarbon accumulations. History Newcomers to South Texas are often amazed that active entry is possible in a district that has produced uranium for over 20 years. Understanding the conditions and occurrences of the past would explain why the opportunity still exists for companies not now active in South Texas to become active. Uranium was discovered in the middle 1950's in sandstone units of the Jackson Group at Tordillo Hill in Karnes County. This discovery was followed by a rush involving most of the major uranium exploration companies as well as several of the not-so-major. Those western prospectors who were used to numerous outcrops and neat land subdivisions were further discouraged by the small size and low grade of the deposits. Then after a brief blast, they left South Texas as they found it and returned to the richer diggings of New Mexico and Wyoming. Susquehanna Western was the only one to stay and develop mines in the area. Eventually they discovered enough ore along the Jackson outcrop to warrant constructing a small mill. They managed, with limited budget and diligent effort, to find enough ore to keep the mill going and eventually expanded into exploration in other formations. By the late 1960's, Susquehanna was mining from both the Jackson and Oakville deposits. About this time, the oil companies began to enter the uranium industry and found, that because of sound forward planning, they controlled the uranium on vast tracts of acreage. At this time, which was more than ten years after discovery, there was so little literature on South Texas uranium deposits that the oil companies began following the known trends and off-setting known orebodies. This, and a few kicks on some well gammaray logs, lead to the discovery of new areas in formations that previously had n o uranium discoveries. Still, the following of the trend as it crossed from one formation to another was the main geologic guide. Nowadays, we in South Texas feel that science has entered into the quest to discover new orebodies. The work of Galloway has indicated new pathways to explore. The understanding of multiple stages of oxidation and reduction has created some doubt about areas drilled in the past and abandoned. The expanded use of oil well logs and geochemical prospecting has lured the more progressive exploration companies off the mineral trend and into unexplored areas. Prognostication The fact that uranium exploration in South Texas has been active for only the past ten years is not an indication that South Texas is not a major uranium district. The geology of the South Texas uranium deposits as described here serves only to indicate that similar geology extends in all directions from the known mineral trend as can be seen on Figure 2.

Jan 1, 1979

By R. W. Heckel, R. A. Tanzilli

ANALYTICAL results have previously been presented for the diffusion-controlled solution of a second phase in a finite medium for planar, cylindrical, and spherical geometries.' These results were obtained by numerical methods using digital computer techniques and are applicable not only to the stage of the problem where the unstable phase shrinks to zero size, but also the subsequent stage where the concentration gradients in the matrix phase become negligible (essentially complete homogenization). It is anticipated that the results of such an analysis may be of use to those workers who are interested in the processes

Jan 1, 1970

By J. P. Witherow

Mr. BIRKINBINE's description of the bad working and sudden chilling of the Warwick Furnace last summer, seems to me quite phenomenal in blast-furnace practice. During my connection with the management of blast furnaces for many years, in the anthracite, cake, and raw-bituminous coal districts, such a me has never come under my notice. It seems to me that the scaffold in the zone of fusion could not have established itself (so that the whole power of the engines, with a blast pressure ranging from 12 to 18 pounds per square inch, could not penetrate), unless the furnace was previously badly scaffolded and bridged in some of its upper sections, from 15 to 30 feet above the hearth level, either in the zone of chemical action or the beginning of the zone of fusion. Such a 'barrier to the upward gaseous currents would cause a suspension of combustion which may have superinduced the scaffold that is assumed to have existed in the zone of fusion. It is difficult to conceive that an agglomerated mass almost across the section of the lower bosh should have formed all at once, if the furnace was free and porous for the reaction of the gaseous currents, above. Therefore, I think, the Warwick furnace was by no means in as free, open, and fine internal condition at the time the trouble commenced as the description of its regular working would lead us to suppose. I do not question the accuracy of the statements relative to the output of iron, etc I merely claim that the phenomenta, as described, could not have been almost instantaneously developed, unless there had been an incipient scaffold and lodgment above the zone of fusion. I would state my hypothesis to be that the stock lodged or collected in some of its upper sections during fie process of blowing-in, on which, as a basis, more or less accumulations may .have lodged, and thus, indirectly, caused the formation of the suc-

Jan 1, 1881

By P. R. Celmer, Leonard R. Weisberg

THE principle of fractional crystallization has been successfully used to prepare high-purity (99.999 pct) Ga. Hoffman and Scribnerl removed single crystals of gallium solidifying in a gallium melt, while Zimmerman2 grew single crystals from the melt by the Kyropolous technique. In contrast, attempts at purifying gallium by zone refining have been less successful. ichards, reported that despite the passage of 40 zones through a gallium ingot, there still remained 5 to 70 ppm each of Cu, Fe, Ca, Mg, Si, Al, and Ag. Previously, Detwiler and Fox4 detected only one impurity, Pb, segregating in zone-refined ingots. These surprising results prompted an investigation of the factors controlling impurity segregation in gallium. Possible reasons for this were insufficient diffusion of impurities in the melt; recontamination of the melt by its oxide film which is not affected by the passage of the zone; reaction of gallium with the boat; sudden freezing of gallium following supercooling, especially since gallium easily supercools to and trapping of impurities at grain boundaries. Impurity segregation tests were carried out by directionally freezing gallium using the Bridgman rnethd, modified in that the molten gallium is lowered out of a furnace into a slush of dry ice and trichloroethylene, thus minimizing supercooling. Since the gallium is contained vertically, the oxide film is in contact only with the tail end of the melt. It was found that Teflon makes an excellent crucible for gallium since it is quite pure, non-reactive, translucent, flexible, machinable, and is not wet by gallium. The gallium crystals could be grown at various speeds, and the melt could be vigorously stirred by a Teflon rod moving through the gallium in a vertical reciprocating fashion. Single crystals could be grown by placing a solid Teflon plug at the bottom of the melt drilled out in such a way to cause the solidifying gallium to follow a winding path. Thus, even if many crystals are originally nucleated, only one grain will predominate. The grain structure of the gallium crystals was revealed by an etchant composed of equal volumes of HC1, HNO3 and HF, diluted with water to half strength. Emission spectrographic analyses were carried out on samples removed from the front and tail ends of the resulting gallium ingots. Typical results of this study are summarized in Table I. The rate of freezing in all three cases was about 1 in. per hr. It can be seen that even though stirring of the melt does help, it is even more important to grow a single crystal of Ga in order to obtain good segregation of impurities. The effect of crys-tallinity on the segregation of impurities was previously observed6 in the directional freezing of germanium; however, in this case, the effect was much less pronounced. This dependence of impurity segregation on the crystalline perfection of Ga may be related to its thermal conductivity which is the most anisotropic of all metals.7 The anisotropic thermal conductivity can cause the solid-liquid interface to be nonuniform, thus leading to trapping of impurities during freeing, and therefore reduced segregation. In conclusion, it is indicated that zone refining of gallium would be more successful if seeding and similar precautions are taken to insure single crystal growth. The authors are indebted to Mr. H. H. Whitaker for the spectrographic analyses and to Drs. B. Abeles and F. D. Rosi for helpful advice and encouragement throughout the course of this work. This research was supported by the Electronics Research Directorate, Air Research and Development Command, under Contract No. AF33(616)-5029. REFERENCES 'J. 1. IToffmon and B. T. Scribrer: I. Research h'atl. Bur. Standards, 1935, "01. 15, p. 205. 'W. Zirnmerman: Science, 1954, vol. 119, p. 41. %J. L. Richards: Nature, 1956, vol. 117, p. 182. 'D. P. Detwiler and W. M. Fox: I. Metals, 1955, "01. 7, p. 205. 5P. W. Bridgman, Proc. Am. ilcod. Sci., 1925, vul. 60, pp. 305,385,423. "S. L1. Christian: private c ommuni cation. 'K. W. Powell: roy. Sac., 1951, vol. 209, p. 525. 'W. G. Pfann: Zone Re fining, p. 20. John Wiley and Sons, Inc., New York, L058.

Jan 1, 1962

A $5000 contract to explore for asbestos in Marinette County. Wis., has been entered into between the Government and the Star Mining Co. of Madison, Wis. The Government will contribute 90 pct or $4500 to the cost of the project. The United States presently produces about 8 pct of its asbestos requirements. "Sulphur stockpiles are at a minimum for national security arid must not be further reduced," was the warning given by L. M. Williams, Jr., president of Freeport Sulphur Co. He stated that although the long-range outlook is favorable , current sulphur production cannot meet the demand and as a result the United States faces a crisis in the coming months.

Jan 12, 1951

By Arthur C. Simmons

Production of oil within the state of Pennsylvania in 1940 was slightly more than the 1939 total, and this increase was due entirely to the new flush Music Mountain field south and west of the main Bradford pool. The influence and magnitude of Music Mountain production will be separately described, inasmuch as it is an important producing unit within the state. Production Bradford Field The production listed herein for Bradford field includes only the part of the field that is within the state of Pennsylvania. Approximately 4000 bbl. per day, or 10 per cent of the total Production of Bradford field comes from Cattaraugus County, New York, and should properly be attributed to production obtained within the New York state area, although locally and economically the Bradford field, situated both in New York State and Pennsylvania, is included as a single statistical unit. The 1940 average production in the Bradford field was 34,831 bbl. per day, as compared with a daily average in 1939 of 35,340 bbl., or a decrease from 1939 of 509 bbl. per day. The decrease in production from the Pennsylvania portion of the Bradford field would have been more pronounced if a portion of the crude from the Music Mountain field were not included with the statistics for Bradford field. The decline can be attributed largely to the fact that more properties of lower average recovery were being drilled in 1939 and 1940 than in previous years, and apparently a subnormal amount of drilling occurred in 1938 and 1939, when about 2100 wells were drilled each year. The full effect of the 1940 drilling is not felt immediately and undoubtedly will affect the producing period of 1941. It appears probable that the water-flood area in the Bradford field has reached a definite peak unless some unusual economic condition should cause abnormal prices and an excessive rate of development such as occurred in 1936 and 1937. Virtually all of the production in the Bradford field was obtained by water-flooding methods, as natural or stripper wells are uneconomical and air and gas repressuring have not proved so efficient as water-flooding as a secondary recovery method. Central and Southern Pennsylvania Central and southern Pennsylvania produced a total of 4,604,763 bbl. of oil during the calendar year of 1940; that is, an increase over the 1939 total of 166,728 bbl. The daily average production was 12,581 bbl., or an increase over 1939 of 422 bbl. per day. Table I includes the total oil production for the state of Pennsylvania for the years 1937 to 1940, inclusive, and the daily average for each of these years. It is impractical to make a complete subdivision by districts, consequently the only segregation is the production from the Bradford field (within the state of Penn-

Jan 1, 1941

By Morris Muskat

TEe method of R. W. Moore' for determining subsurface interfacial depths by means of integrated curves of apparent resistivity has been analyzed theoretically. It is found that the only unique tangents that can be drawn to such curves are the asymptotes at infinite electrode spacing and the tangents through the origin at vanishing electrode spacing. Explicit expressions have been derived for the relationship between the electrode spacing at the points of intersection of these tangents and the thickness of the surface strata as a function of the conductivity parameters for the two-layer and three-layer earths. It is found that in all cases the electrode spacing at the points of intersection will exceed % of the thickness of the surface layer, and may even become indefinitely large as the resistivity of the deepest layers increases as compared with that of the surface layer. These results do not agree with the empirical findings of Moore that the intersection of the tangent lines fall at an electrode spacing very approxirnately equal to the thickness of the surface layer. Introduction In a recent paper, R. W. Moore1 proposed a new method for the analysis and interpretation of earth-resistivity measurements. This consists essentially in plotting against the electrode separation of a Gish-Rooney system the integral of the apparent resistivity with respect to the electrode spacing, and observing the breaks in the integral curves. Specifically, tangents are drawn to the various segments of the integral curves, which show appreciably different slopes, and the intersections of these tangents are used as indications of the depths of the various underlying strata. By numerous examples Moore has shown that the electrode separation at the first intersection so found agrees very closely with the depth of the bottom of the surface layer. Moreover, in a number of instances the intersections for greater electrode spacings seemed to correspond to the depths of deeper beds. From a strictly empirical point of view, the procedure proposed and demonstrated by Moore appears to be particularly interesting because of its simplicity as well as its apparent accuracy, Moreover, such a simple method would be especially valuable in view of the well-known difliculties heretofore encountered in the quantitative interpretation of resistivity data. It therefore seems appropriate to attempt a mathematical analysis of the problem to see whether the integral method of Moore has a sound basis. Such an analysis is presented here. Even on cursory consideration, it is clear that the remarkable successes observed by Moore in the application of his method are indeed surprising. For it depends upon the determination and choice of the slopes of smooth and continuous curves, which by their nature must show even more gradual- variations than the original apparent-resistivity plots that are already so difficult to interpret quantitatively. It is well established, of course,

Jan 1, 1946

By Morris Muskat

TEe method of R. W. Moore' for determining subsurface interfacial depths by means of integrated curves of apparent resistivity has been analyzed theoretically. It is found that the only unique tangents that can be drawn to such curves are the asymptotes at infinite electrode spacing and the tangents through the origin at vanishing electrode spacing. Explicit expressions have been derived for the relationship between the electrode spacing at the points of intersection of these tangents and the thickness of the surface strata as a function of the conductivity parameters for the two-layer and three-layer earths. It is found that in all cases the electrode spacing at the points of intersection will exceed % of the thickness of the surface layer, and may even become indefinitely large as the resistivity of the deepest layers increases as compared with that of the surface layer. These results do not agree with the empirical findings of Moore that the intersection of the tangent lines fall at an electrode spacing very approxirnately equal to the thickness of the surface layer. Introduction In a recent paper, R. W. Moore1 proposed a new method for the analysis and interpretation of earth-resistivity measurements. This consists essentially in plotting against the electrode separation of a Gish-Rooney system the integral of the apparent resistivity with respect to the electrode spacing, and observing the breaks in the integral curves. Specifically, tangents are drawn to the various segments of the integral curves, which show appreciably different slopes, and the intersections of these tangents are used as indications of the depths of the various underlying strata. By numerous examples Moore has shown that the electrode separation at the first intersection so found agrees very closely with the depth of the bottom of the surface layer. Moreover, in a number of instances the intersections for greater electrode spacings seemed to correspond to the depths of deeper beds. From a strictly empirical point of view, the procedure proposed and demonstrated by Moore appears to be particularly interesting because of its simplicity as well as its apparent accuracy, Moreover, such a simple method would be especially valuable in view of the well-known difliculties heretofore encountered in the quantitative interpretation of resistivity data. It therefore seems appropriate to attempt a mathematical analysis of the problem to see whether the integral method of Moore has a sound basis. Such an analysis is presented here. Even on cursory consideration, it is clear that the remarkable successes observed by Moore in the application of his method are indeed surprising. For it depends upon the determination and choice of the slopes of smooth and continuous curves, which by their nature must show even more gradual- variations than the original apparent-resistivity plots that are already so difficult to interpret quantitatively. It is well established, of course,

Jan 1, 1946

By Arthur C. Simmons

Production of oil within the state of Pennsylvania in 1940 was slightly more than the 1939 total, and this increase was due entirely to the new flush Music Mountain field south and west of the main Bradford pool. The influence and magnitude of Music Mountain production will be separately described, inasmuch as it is an important producing unit within the state. Production Bradford Field The production listed herein for Bradford field includes only the part of the field that is within the state of Pennsylvania. Approximately 4000 bbl. per day, or 10 per cent of the total Production of Bradford field comes from Cattaraugus County, New York, and should properly be attributed to production obtained within the New York state area, although locally and economically the Bradford field, situated both in New York State and Pennsylvania, is included as a single statistical unit. The 1940 average production in the Bradford field was 34,831 bbl. per day, as compared with a daily average in 1939 of 35,340 bbl., or a decrease from 1939 of 509 bbl. per day. The decrease in production from the Pennsylvania portion of the Bradford field would have been more pronounced if a portion of the crude from the Music Mountain field were not included with the statistics for Bradford field. The decline can be attributed largely to the fact that more properties of lower average recovery were being drilled in 1939 and 1940 than in previous years, and apparently a subnormal amount of drilling occurred in 1938 and 1939, when about 2100 wells were drilled each year. The full effect of the 1940 drilling is not felt immediately and undoubtedly will affect the producing period of 1941. It appears probable that the water-flood area in the Bradford field has reached a definite peak unless some unusual economic condition should cause abnormal prices and an excessive rate of development such as occurred in 1936 and 1937. Virtually all of the production in the Bradford field was obtained by water-flooding methods, as natural or stripper wells are uneconomical and air and gas repressuring have not proved so efficient as water-flooding as a secondary recovery method. Central and Southern Pennsylvania Central and southern Pennsylvania produced a total of 4,604,763 bbl. of oil during the calendar year of 1940; that is, an increase over the 1939 total of 166,728 bbl. The daily average production was 12,581 bbl., or an increase over 1939 of 422 bbl. per day. Table I includes the total oil production for the state of Pennsylvania for the years 1937 to 1940, inclusive, and the daily average for each of these years. It is impractical to make a complete subdivision by districts, consequently the only segregation is the production from the Bradford field (within the state of Penn-

Jan 1, 1941

By R. Scot Clark

The reactively sputtered silicon dioxide capacitor -was developed for use in the monolithic integrated circuit, thereby requiring the capacitor to be fabricated on an oxidized silicon slice. The silicon dioxide film is formed by reactively sputtering silicon in a 50 pct Ar-50 pct 0, atmosphere and the physical properties are indistinguishable from silica. A practical upper limit of capacitance per unit area of 0.25 pf per sq mil is reached with the capacitors fabricated from the Si0, film. Methods shown to enhance this value are double stacking the thin-film capacitors and addition of aluminum to the silicon cathode during sputtering to form an aluminosilicate dielectric. A major contribution to the field of diffused integrated circuits would be the addition of auxiliary passive devices for replacement of diffused passive devices which are currently being fabricated for many integrated circuits. This accomplishment would increase the flexibility of the diffusion process in order to concentrate more on transistor parameters rather than on fabricating diffused resistors and capacitors. To pursue this technique, a thin-film SiOz capacitor was developed which has _ proven applicable to many integrated circuits. Although the SiOl capacitor has an application, the major deterrent from extending the integrated circuit into many useful areas such as low-frequency linear application is the low dielectric constant of SiO, and the low usable capacitance in an integrated circuit. This paper will cover the sputtering techniques used for forming the SiO, film, the physical and electrical properties of sputtered SiO,, and yield information concerning the application of these capacitors to integrated circuits. REACTIVE SPUTTERING Reactive sputtering is simply the sputtering of a metal or semiconductor in glow discharge in the presence of a reactive gas. The material to be sputtered is seen in Fig. 1 as the cathode of the system and is bombarded with positively charged ions of the ambient gas. In this investigation, the ambient gas is composed of 50 pct Ar and 50 pct O2 at a pressure of approximately 2.5 X l0-' Torr. The ions are accelerated toward the cathode in the cathode dark space by the electric field and upon striking the cathode effect a momentum energy transfer to the surface atoms. The transferred energy is sufficient to dislodge a surface atom or atoms and these particles diffuse through the glow discharge to the collector or anode. Several mechanisms of oxidation in the reaction chamber can be considered during reactive sputtering. 1) The surface of the cathode is oxidized and the oxide is subsequently sputtered. 2) Oxidation and sputtering occur simultaneously. 3) Sputtering of the cathode material is followed

Jan 1, 1965