Search Documents

By T. E. Seidel, A. U. MacRae

The dependence of the electrical and crystalline properties of silicon containing ion implanted boron atoms have been studied as a function of the incident dose, substrate temperature, and annealing tempera-ture. Hall effect studies show that the compensation due to defects is negligible after annealing at and above 500°C for a dose of 1013 ions per sq cm. Steps occur in the isochronal annealing curve for the sheet resistance at 300°C and 800°C and the mechanisms responsible for these steps are discussed. The range of the ions at 150 kev is 3500 * 5001. Electron diffraction studies on samples implanted with 150 ker ions show the existence of damaged (polycrystalline) silicon closer to the surface than the range of the ions. Etching and subsequent annealing of etched and unetched specimens suggest that the poly crystalline silicon is closer to the surface than the bulk of the distribution of ions. THE purpose of this study is to investigate some electrical and crystalline properties of ion implanted boron in silicon. Sheet resistance, Hall measurement, depth distribution by chemical staining, thermal probe and electron diffraction have been used to study the properties of samples implanted in a random direction with ions having energy up to 150 kev. The boron-silicon system has been the subject of considerable study'-7 due to its possible application in the fabrication of electronic devices. The implanted ions produce considerable crystalline damage to the substrate crystal before they lose most of their primary energy and come to rest. Fortunately, most, if not all, of this damage can be removed by subsequent annealing or by holding the substrate at an elevated temperature during the implantation process. Sheet resistivity measurements of the p-type layers produced by boron implantation into room-temperature silicon, reveal that the annealing occurs in a two-step process: the first occurring at -300°C and the second at -800°C.' Electron-microscope and low-angle electron diffraction studies of this damaged material indicate that the bombarding ions produce an amorphous silicon region about the trajectory of each ion.' At high doses, these damaged regions overlap and an amorphous surface layer results. Furthermore, the 800°C annealing step, appears to be associated with the elimination of this gross damage. The depth distribution of the as-implanted and also the annealed samples have been studied by an angle lap and staining technique as well as by Hall measurements.3-7 We find the experimentally determined ranges of the boron are less than those calculated by the Lindhard-Scharff-Schiott theorys (hereafter referred to as the LSS theory). Our results are in essential agreement with pre- vious results. In addition, we have made Hall measurements on samples bombarded with a low dose (2 x 1013 ions per sq cm) to minimize impurity banding effects, and find that deep ionized levels influence the carrier concentration and room-temperature hole mobility until the sample is annealed at temperatures above 500°C. Above this temperature, the data corresponds to that obtained when silicon is doped with boron by conventional techniques. We have also made a depth distribution determination of the crystalline damage due to the implanted boron by using glancing angle electron diffraction techniques. It was found that the gross damage depth distribution of heavily implanted samples is closer to the surface than the depth distribution of the electrically active boron. By removing this gross damage, without affecting the distribution of the implanted boron, we have determined that the 800°C annealing stage is not exclusively due to the improvement in the crystalline perfection of the amorphous material but also appears to be associated with the annealing of some point defects. These results and their relation to previous results are discussed in the following sections. IMPLANTATIONS Boron ions were implanted into silicon samples using an accelerator capable of operating from 10 to 150

Jan 1, 1970

By W. A. Ver Wiebe

UNder the impetus of new demands caused by the defense program, the oil and gas industries of Kansas established new records during the year 1941. In all, 2113 wells were drilled, which compares favorably with the record total drilled in 1937. These 2113 tests resulted in 1446 oil wells, 76 gas wells and 592 dry holes. In all three categories there was an increase over the previous year, but unfortunately the most marked increase was in the dry holes. Nearly 80 per cent of the increase must be allocated to the drilling 01 unsuccessful tests. This was partly because of the increasing difficulty of finding new reserve areas and partly because of the erratic character of the production in the Arbuckle dolomite, which is now the main producing zone. Closer analysis of the totals reveals that western Kansas accounted for 1634 tests, of which 1186 were oil wells, 34 were gas wells and 415 were dry holes. The total potential initial daily production uncovered by the successful wells amounted to 1,691,000 bbl. of oil and 508,000,000 cu. ft. of gas. Both figures indicate a considerable decrease when compared with the proceeding year; in 1940 the respective figures were 2,128,000 bbl. and 1,289,000,000 cu. feet. In eastern Kansas a total of 479 wells were drilled. Among these, 260 were oil wells accounting for a daily initial potential production of 45,662 bbl. The new gas wells numbered 42 and added 290,438,000 cu. ft. per day to the gas potential production of the state. The remaining tests, 177 in number, were dry. It is interesting and significant that almost half (791) of the total wells drilled in western Kansas were drilled by the independent operators. Among the large companies the Cities Service Oil Co. drilled 169 wells; the Stanolind Oil and Gas CO., 101; the Skelly Oil Co., 80; the Continental Oil Co., 99, and the Shell Petroleum Co., 63 wells. In eastern Kansas the independent operators drilled 406 out of the total of 479 wells. Among the major oil companies the Cities Service Oil Co. drilled 38; the Phillips Petroleum Co., 13, and the Sinclair-Prairie Oil Co., II wells. The figures on relative percentages of dry holes to successful oil or gas wells are revealing. In western Kansas approximately one third of all wells drilled by the independent operators were dry holes. The major oil companies drilled approximately 844 wells in western Kansas, of which 678 were successful in finding either oil or gas. It thus appears that the major companies fared much Getter than the independents. In eastern Kansas the major companies drilled 73 wells of which 63 were successful in finding commercial quantities of oil or gas. No less than 286 wildcat tests were put down in western Kansas and 72 in eastern Kansas, or 358 in all, during 1941. Considerably more than half of these were drilled by independent operators; zoo in western and 66 in eastern Kansas. An exploratory hole % mile or more from production is regarded as a wildcat well in Kansas. On a percentage basis, approximately 75 per cent of all wildcat wells were failures; only 25 per cent found oil or gas in western

Jan 1, 1942

By W. A. Ver Wiebe

UNder the impetus of new demands caused by the defense program, the oil and gas industries of Kansas established new records during the year 1941. In all, 2113 wells were drilled, which compares favorably with the record total drilled in 1937. These 2113 tests resulted in 1446 oil wells, 76 gas wells and 592 dry holes. In all three categories there was an increase over the previous year, but unfortunately the most marked increase was in the dry holes. Nearly 80 per cent of the increase must be allocated to the drilling 01 unsuccessful tests. This was partly because of the increasing difficulty of finding new reserve areas and partly because of the erratic character of the production in the Arbuckle dolomite, which is now the main producing zone. Closer analysis of the totals reveals that western Kansas accounted for 1634 tests, of which 1186 were oil wells, 34 were gas wells and 415 were dry holes. The total potential initial daily production uncovered by the successful wells amounted to 1,691,000 bbl. of oil and 508,000,000 cu. ft. of gas. Both figures indicate a considerable decrease when compared with the proceeding year; in 1940 the respective figures were 2,128,000 bbl. and 1,289,000,000 cu. feet. In eastern Kansas a total of 479 wells were drilled. Among these, 260 were oil wells accounting for a daily initial potential production of 45,662 bbl. The new gas wells numbered 42 and added 290,438,000 cu. ft. per day to the gas potential production of the state. The remaining tests, 177 in number, were dry. It is interesting and significant that almost half (791) of the total wells drilled in western Kansas were drilled by the independent operators. Among the large companies the Cities Service Oil Co. drilled 169 wells; the Stanolind Oil and Gas CO., 101; the Skelly Oil Co., 80; the Continental Oil Co., 99, and the Shell Petroleum Co., 63 wells. In eastern Kansas the independent operators drilled 406 out of the total of 479 wells. Among the major oil companies the Cities Service Oil Co. drilled 38; the Phillips Petroleum Co., 13, and the Sinclair-Prairie Oil Co., II wells. The figures on relative percentages of dry holes to successful oil or gas wells are revealing. In western Kansas approximately one third of all wells drilled by the independent operators were dry holes. The major oil companies drilled approximately 844 wells in western Kansas, of which 678 were successful in finding either oil or gas. It thus appears that the major companies fared much Getter than the independents. In eastern Kansas the major companies drilled 73 wells of which 63 were successful in finding commercial quantities of oil or gas. No less than 286 wildcat tests were put down in western Kansas and 72 in eastern Kansas, or 358 in all, during 1941. Considerably more than half of these were drilled by independent operators; zoo in western and 66 in eastern Kansas. An exploratory hole % mile or more from production is regarded as a wildcat well in Kansas. On a percentage basis, approximately 75 per cent of all wildcat wells were failures; only 25 per cent found oil or gas in western

Jan 1, 1942

By John W. King

Uranium ore was first discovered in the Edgemont district of the southern Black Hills in the summer of 1951. The discovery was not made known for some time, but after the news leaked out prospecting became intense, and several hundred claims were staked in the spring of 1952. The Hot Springs Sub Office of the Atomic Energy Commission was established at that time and airborne radiometric surveys were commenced by the Government and by private companies. During the succeeding summer another important discovery was made by private airborne surveys in the northern Black Hills, and the area favorable for uranium ore was expanded many times. Between that summer of 1952 and the present, many individuals and groups have explored, developed, and exploited their claims until now uranium ore is produced in significant quantities and substantial reserves have been developed. The Black Hills portion of the geologic map of the U. S. issued by the U. S. Geological Survey is shown in Fig. 1. Sedimentary formations are exposed as a series of cuestas and hogbacks in a roughly annular pattern with the older sediments resting on the pre-Cambrian core, which is exposed in the eastern and southern portions of the dome.

Jan 1, 1956

By Carl G. Schwenk

Rocks of the Precambrian Shield of Rusk County, Wis., were recognized as a favorable host for volcanogenic base metal deposits by personnel of Bear Creek Mining Co. Most of the county is covered by a thick layer of glacial drift: consequently, geophysical techniques played a prominent role in the exploration program conceived and initiated there in 1966. The original work on three Precambrian exposures was followed by an airborne electromagnetic survey and subsequent ground follow-up. A geophysical evaluation of air-borne anomaly F-22 defined a target which was interpreted as a massive sulfide body. Numerous potential field and electrical tools were utilized to describe the geometry and physical properties of the target. Drilling confirmed the massive sulfide interpretation and eztentually outlined a 6 million-ton copper deposit.

Jan 1, 1977

By H. G. Schneider

THE Smackover oil and gas field lies in Ouachita and Union Counties, Ark., in the south-central part of the state, in T.15 and 16S., R.15, 16, and 17W. It is 10 miles north of El Dorado, the principal business and railroad center in the south-central part of the state, and extends from the town of Smackover in all directions. Productive territory having an aggregate area of nearly 55 sq. mi. has been developed. It extends 6 miles from north to south and 12 miles from east to west. The field may be divided into two parts: the east district, which includes the area east of the town of Smackover, and the west district, which includes the area west of the town of Smackover. In relation to the neighboring productive fields of Arkansas, the Smackover field is 9 miles north of .the El Dorado oil and gas field, 8 miles slightly west of north of the East El Dorado oil and gas field, and 16 miles east of the Stephens oil field. Smackover was discovered in May, 1922, when the Oil Operators Trust drilled well No. 1 on the J. T. Murphy farm, in the southeast quarter of sec. 8, T. 16S., R.15W. This well is located almost, on the top of the Norphlet dome and was drilled to the Nacatoch sand. It had an initial open flow volume of 30,000,000 cu. ft. of dry gas per day, and a rock pressure of 950 lb. per sq. in. In July, 1922, the V. K. F. Co. completed the first oil well in sec. 29, T.15S., R.15W., on the north side of the Norphlet dome, and 3 miles north of the first gas well. This well started the active development of the north and northwest sides of the dome.1

Jan 3, 1924

Jan 1, 1938

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

The subjects of this study are two corrosion phenomena familiar to operators of aluminum plants employing Soderberg anodes of the vertical type, namely the sul-fide scale formation observed at the steel contact spikes and the corrosion wear observed at the lower edge of the gas collecting skirts. The causes of these corrosion phenomena are discussed on the basis of observations from practice and measurements on commercial cells as well as on laboratory experiments. It is concluded that the anode spike corrosion is mainly due to the attack by sulfur compounds contained in the anodically evolved gases and that this attack is greatly promoted by cracks and pores in the anode carbon embedding the lower spike ends. The corrosion of the gas collecting skirt is mainly attributed to anodic dissolution of the iron during occasional contacts with the melt. ANODE SPIKE CORROSION The visible result of this corrosion is the formation of a brittle loosely adherent scale on the lower ends of the mild steel spikes maintaining the electric contact to the carbon anode, Fig. 1. The thickness of the scale usually varies from 0.5 to 3 mm, but in some cases scale of about 10 mm thickness has been observed by the writers. During the spike pulling, usually repeated every 3 weeks, part of the scale often loosens and remains in the anode carbon, resulting in contamination of the aluminum with iron. This corrosion has been attributed to reaction of the iron with gaseous sulfur compounds originating from the anode paste materials.'-4 This paste usually consists of 70 pct precalcined petroleum coke with 1.2 to 1.4 pct S and 30 pct coal tar pitch containing 0.5 to 0.7 pct S. During operation the gasification of the anode materials takes place in two ways: First, gases are evolved by the gradual baking of the anode paste added on top of the anode. Due to the sealing effected by the upper semifluid zone of the paste, these gases, containing sulfur compounds from the pitch, are forced downward through pores and cracks in the rigid anode carbon. At the temperatures of the zone of the lower ends of the spikes, 700" to 900°C, the original components of the baking gas must undergo decomposition, similar to that taking place with the production of coal gas, resulting in a gas mixture consisting mainly of H2 and CH4 with small percentages of H2S as the main sulfur compound.5 Second, the anodic reaction results in a mixture of C02 and CO, the total quantity of which is about 15 times that of the baking gas. These anode gases must carry the entire sulfur content of the carbon gasified by the anodic reaction. Henry and Holliday6 have shown that COS is the main sulfurous component of the anode gases from Soderberg cells. Soderberg anodes usually exhibit a network of vertical cracks, frequently traversing from one spike to the next one and to the outside of the block and widening downward to the working face of the anode. In addition the anode carbon, particularly that below the spike ends, is rather porous, as indicated in Fig. 1. It therefore seems probable that the anode gases also may partly penetrate to the spike ends. As the anode is partly immersed in the melt, the static pressure of this must forward this penetration. I) SPIKE SCALE COMPOSITION A great number of freshly extracted spikes from industrial plants were inspected and samples of the scale collected for examination. Before analyzing the samples a thin iron oxide layer, formed by air oxidation of the outside of the red hot scale immediately after spike pulling, was removed. On the average the Fe/S ratio found by these analyses corresponded to I the composition FeSl. oo7. X-ray powder patterns showed no oxide and otherwise agreed with those found by Haraldsen7 for iron sulfide with 50.00 at. Pct

Jan 1, 1970

By G. Sherburne Rogers

One of the features of oil-field work that puzzles operator, chemist, and geologist alike, is variation in the gravity of the petroleum produced on neighboring leases or even from adjoining wells. Few fields in the United States yield oil that is of uniform gravity throughout; in some fields the different grades are produced from different sands, in a few from different formations, and in many from different areas in the same sand. In a few cases, perhaps, a common assumption—that the heavier oil is derived from the lighter through the escape of the more volatile constituents—is valid, but many cases can not be explained in this way. Although in the California fields the specific gravity of the oil generally decreases with depth, there are numerous exceptions to this rule; and, as in many other regions the light oil is found nearest the surface, it is evident that evaporation underground is generally an unimportant factor. It is generally recognized that the great differences between petroleum from widely separated fields are due largely to differences in age and degree of metamorphism and to variation in the composition of the original organic matter; but in the writer's opinion some of these broader differences, as well as most of the minor variations in the character of the oil from any one field, are due to the local action of natural reagents such as sulphur or oxygen. This is particularly likely to be true if the oil has migrated from one formation to another, as in the California fields; and in some arcas it appears that variation in sulphur content may even afford a rough index of the extent or distance of the migration. It is the purpose of this paper to call attention to the chemical action of sulphur and oxygen on petroleum, to show that the gravity of the oil from any one field is intimately related to its sulphur content, and to discuss the possi-

Jan 1, 1918

Jan 1, 1932

By G. A. Guess

THIS investigation was started with the idea of determining whether copper-nickel mattes might not have a lower flowing temperature than copper mattes, and thus perhaps aid in accounting for the difficulty so far experienced in attempts at pyritically smelting copper-nickel ores. We have used the term flowing temperature to avoid confusion with the usual melting temperature. The idea at first was that there might be a greater viscosity range in the one matte than in the other. In the early experiments it was in our minds to determine the relative fluidity of the mattes at a given temperature. Looking to this end we tried pouring equal quantities of matte at the same temperature down an inclined graphite slab, and comparing the distances traveled. Results from such experiments were not satisfactory. We next tried pouring equal quantities at the same temperature through a drilled hole in an Acheson graphite crucible, timing the flow with a stop watch, the whole operation being carried out in the muffle. The flowing temperatures of the mattes tried in this way appeared to be about the same, and there was no marked difference in their fluidity when well fused. Oxidation gave some trouble. These experiments finally led to the adoption of the following apparatus which we thought at the time was wholly original with us, but which we have since found was described by W. McA. Johnson.' The tray used was a slab of graphite 8 in. long, 2 in. wide and ¼ in. thick. It had six holes, into each of which sat a cup of Acheson graphite. Centrally in the bottom of each cup was a vertically drilled hole 3/16 in. in diameter and ½ in. long. The mattes to be tested were put into the cups, in a solid piece. The cups were covered with inverted Battersea "A" cups. The tray was put into the muffle of a gas-fired furnace. Supports on .each end held the tray about 2 in. from the floor of the muffle. Udder

Jan 6, 1916

R. C. Canby, Wallingford, Conn. (communication to the Secretary*). —Apropos of the experimental reduction of copper from cuprous chloride by fusion with ground limestone and colre, as described by Messrs. Laist and Frick, and also proposed for use at Chuquicamata, it might be of interest to refer bricfly to the experience at Argentine, Kan., in the smelting of the suboxide of copper (as produced in the Hunt and Douglas process) containing appreciable quantities of chlorides. In the Engineering and Mining Journal of June 10, 1911,I gave some account of what had appeared to be crucial difficulties with the Hunt and Douglas process, and how the filter-press difficulty had been so rapidly overcorne after my discovery of the effect of the sodium salts in the leaching solutions. I also described the effect of the cupola-furnace gases upon the lime rock with which I had replaced the coke in the absorption tower, which apparently showed the presence of considerable chlorine, due to the imperfect conversion of the subchloride to suboxide, as well as that due to the difficulties of washing thoroughly the suboxide with the means provided, and also to the presence of chlorides in the cement copper which was smelted with the suboxide. The fumes from the cupola, when issuing direct into the atmosphere, were very dense and white, except when a hot furnace top caused a reddish tinge due to dust. These fumes had a peculiarly suffocating effect, SO that when they were blown over into the town the population suffered the greatest actual distress, not the mere annoyance which would have been due to a disagreeable odor. The absorption tower had been built at the instance of the city authorities to abate this nuisance, and not with the idea of making any additional metal savings. A serious feature in connection with the Argentine experience with the Hunt and Douglas process was, that it had been implicitly assumed that there could be no metal loss in the Hunt and Douglas process itself, and that all attempts to locate the ruinous copper losses which were accumulating in the metallurgical accounts were devoted to the roasting department. It is possibly unfortunate for metallurgical advance along these particular lines that just about the time of this discovery of this previously unsuspected volatilization loss, in the smelting of the suboxide, the Kansas City company made a contract with the Western Union Telegraph Co. for its supply of copper sulphate and the Hunt and Douglas

Jan 1, 1915

By F. W. C. Boswell, R. L. Cunningham, H. M. Weld

Chemical analysis shows the partition of the magnesium addition between the metal and the graphite is independent of whether the graphite is in the form of nodules or flakes. The bright central spot observed in nodular graphite polished sections is shown to be due to the structure of the nodules. DURING the past few years numerous papers have been published on the production1-7 and heat treatment" of nodular cast irons. However, very little information is available on the structure of the nodules and the reason for their formation. It would appear that an explanation of the phenomenon of nodulation must await a detailed knowledge of the nature of the nodule. Disagreement exists among various workers on such a fundamental point as to whether or not a nodule actually contains a microscopically visible, nongraphitic nucleus.9-11 Work was initiated with a view to obtaining definite information on this and other aspects of the problem. Chemical Separation and Analysis Microscopic appearance had indicated9-11 that a nongraphitic core might exist in nodules (Fig. 1). It appeared that a chemical comparison of separated nodules and flake graphite would be profitable, for if the core is nongraphitic a relatively large amount of certain elements would be found in the nodules as compared to the flake. This comparison could best be made by obtaining nodules and flake from the same melt of cast iron, part of which had been in-noculated with a suitable addition reagent for the formation of nodules. A 300 lb melt was produced. About half of this was innoculated in the ladle with an Fe-Si-Mg alloy to produce nodules and cast into keel blocks; the remaining half of the melt had silicon added in an effort to compensate for the silicon in the innoculant used in the other half of the melt and this was cast into similar keel blocks. The analyses of the resultant irons are given in Table I. Nodules and flake were chemically extracted from 2 kg samples of metal as described in the appendix. While this method dissolved the iron and chromium carbides, it did not dissolve the titanium, vanadium, and molybdenum carbides. These latter carbides could have been removed by nitric acid, but in other experiments it was found that it attacked pools of metallic iron entrapped in the nodules which had, until the nitric acid treatment, been protected from the attack of the sulphuric, hydrochloric, and hydrofluoric acids. It will be shown in the next section that entrapped iron exists in nodules but not in flake. On microscopic examination many tiny irregular particles were observed to accompany both the nodules and the flake. These were identified by tabling a sample of nodules from which a sufficient fraction was obtained for X-ray analysis. A good pattern of titanium carbide was obtained indicating that this was the predominant compound present. Since it was not possible to determine how completely the carbides could be removed mechanically and since their removal from flake is much more difficult, it was decided not to resort to any separation as this would render further comparisons more difficult. The samples were ashed in a combustion

Jan 1, 1953

By W. F. Hower, W. Brown

Large-scale sand consolidation tests were conducted in an effort to determine the reasons for the successes and failures of this method of sand control. Several different consolidating materials were used in treating both clean and bentonitic sands that were packed in a chamber having a capacity of 3.3 cu ft. The results were essentially the same for all of the different consolidating materials, The data show that low-viscosity consolidating materials pumped at a relatively slow rate gave the best results. Where the formation has produced sand, the treating fluids can compress the formation, thus permitting the channeling of fluids to another horizon. Pressure-packing these zones before attempting to consolidate is recommended. Sands containing more than 4 per cent of water-swelling clays are not good candidates for consolidation. It is indicated that loose sand, particularly when it is bentonitic, can be fractured during the placement of the treating fluids. INTRODUCTION Sand production in oil and gas wells has plagued the industry for many years, and numerous cures for this problem have been suggested. Most methods have been successful to a certain degree, but the great variety of well conditions that exist in the different areas has magni- fied the problem and limited the successful use of the various systems. Four review papers1-4 present a wealth of information concerning the degrees of success that have been obtained by the different sand-control methods. The bridging of sand grains by the use of gravel packs and screens has been quite successful. However, these methods do not leave the casing clear for all types of multiple completions, and the cure does not last for the production life of the well in some instance:;. The control of loose sands by sand consolidation with resins has never been as successful as desired. It has always been hoped that such a treatment would eliminate all sand problems for the life of the well, but. initial applications, starting in the middle 1940's, were only moderately successful. Lott, et a1,3 reported a success ratio of approximately 50 per cent and made the following conclusions. The highest percentage of successes were obtained where: a. Consolidation of a zone was made at the time of initial completion or prior to the production of sand. b. The interval treated was less than 12 ft in length. c. Between 30 and 50 gill plastic/ft of producing interval was displaced through the perforations. REASONS FOR SAND CONSOLIDATION FAILURES Our own experiences in the field of sand consolidation point toward the following conditions as the major reasons for the failure of sand consolidation attempts. 1. Mud-plugged perforations and mud invasion of the formation. 2. Sand in the casing covering all or part of the perforations. This sand could be either formation sand or one of the coarser sands used as propping agents in hydraulic fracturing. 3. Holes in the casing. 4. Channels behind the casing. 5. Attempting to treat too long a perforated section. 6. Too high a percentage of water-swelling clays in the formation. 7. Formations that have produced sand. Recent attempts were made to treat perforated sections ranging from 10 to 30 ft, in wells that have produced sand, by using a straddle packer that was raised and lowered through the perforations as the consolidating material was being pumped. In most instances, the pressure required to pump fluid into the formation varied considerably as the tool was raised and lowered. This suggested the possibility that significant differences in permeability were present or that only part of the formation had produced sand. There were times when a sudden break in pressure indicated that a fracture was being formed. Research conducted several years ago concerning the problem of the control of water in air and gas drilling indicated that shale sections could be fractured quite easily. In addition, it was determined that it was easier to pump fluids into shale bodies by fracturing the shale itself, or the interface between the shale and sand, than to pump into a fluid-saturated formation. Formations that produce sand are usually adjacent to shale bodies and frequently have shale streaks of various thicknesses inter-bedded in the sand. Therefore, where shale is exposed to fluid pressure it

By P. G. Shewmon, H. E. Collins

We have studied the effect of adsorbed sulfur on the surface self-diffusion of copper using eight diflerent surface orientations and the grain boundary grooving method. The eight orientations studied were the four lying near the low-index surfaces—(loo), (Ill), and two directions in the (110)-plus four higher-index surfaces. Surface-diffusion measurements were made over a range of HZS concentrations (in Hz) from 3 to 1500 ppm between 830°and 1050°C. The results can be divided into two groups—Group 1 contains the two (110) surfaces while Group 2 contains the remaining six surfaces. In Group 1, increasing the temperature increases the effect of Hz S on DS for the Hz S range 5700 ppvn. Qs and Do increase with increasing H2S concentration in this Hz S range. Beyond this range, increasing the temperature decreases this effect on D,; also Q, and Do decrease. In Group 2, increasing the telnperature decreases the effect of H2 S on D, for the H2S range studied, and Qs and Do decrease with increasing Hz S concentration. In any study of surface phenomena, there invariably arises the question of the possible presence of and effect of adsorbed impurities. Such questions are well-founded since the presence of adsorbed atoms can sometimes produce marked changes in the kinetics of surface-energy-driven processes. In the last few years, values of the surface self-diffusion coefficient, D,, have been determined on a variety of metals by studying the decay of scratches or the growth of grain boundary grooves.L~3-L0~L3 Yet there has been relatively little work done in which the concentration of an adsorbed impurity was systematically varied and the effects observed. Work of this sort would provide some basis in fact for the assertions often made about the ro1.e of adsorbed impurities in the differences between the results of different workers in different atmospheres and on different metals. It also is relevant to those cases in which surface monolayers produce profound effects in commercially important processes. The most marked example of such effects is the ability of nickel or palladium to increase the sintering rate of tungsten by many orders of magnitude.' The aim of this work was to study the effect of sulfur partial pressures on the surface self-diffusion of copper. It was felt that this in conjunction with a study of the degree of adsorption and type of active sites involvedL8 would provide a wide range of data for one system and hopefully lead to some insight into the mechanism by which sulfur adsorption influences copper diffusion. The main reasons for choosing the Cu-S system were, first, faceting was reported not to accompany the adsorption of sulfur. This is required if our experimental technique is to work. Second, Oudar has determined a high temperature adsorption isotherm for this system, an event which puts the Cu-S system almost in a class by itself.I4 EXPERIMENTAL PROCEDURE Initially, we considered studying the effect of an adsorbed impurity on surface self-diffusion of copper using isolated (or single) scratch smoothing as the technique and oxygen as the impurity. Copper was chosen as the material because the effects of orientation and anisotropy of the surface self-diffusion coefficient, D,, of copper in a dry hydrogen atmosphere had been studied extensively by Gjostein' and by Shewmon and ~hoi.~,~ The isolated scratch technique was chosen because both the effects of surface orientation and anisotropy of D, in a given surface could be easily studied with this method.~ Oxygen was tried as the impurity because Robertson and Shewmon""~ had studied its adsorption on copper at 1000°C over the range of oxygen partial pressures of 10"22 to 10-l3 atm. After several preliminary runs, it became evident that neither the scratch technique nor the impurity oxygen would be satisfactory for this work. Scratching deforms an annealed surface so that the region near the scratches recrystallizes, thereby disrupting the scratch profiles. One can avoid this by deforming the specimen sufficiently before scratching to give complete recrystallization on subsequent heating.4 However, as a result of Gjostein's success in scratching and annealing undeformed gold single crystals without local recrystallization,13 we attempted something similar with copper single crystals using a 0.7-mil diamond phonograph needle mounted in a Tukon hardness tester. All specimens recrystallized upon being annealed. Also, some copper specimens were sent to Gjostein to be scratched using his technique. The results were the same. As a result, the scratch technique was dropped in favor of the grooving of symmetric grain boundaries. Preliminary work using oxygen showed that faceting began to occur before oxygen adsorption had any measurable effect on D, at 938°C (at Pbo/P, = 0.12). Since heavy faceting would interfere with the measurement, we decided to use a sulfur-containing atmosphere (H2S/H2). Work by Oudar and Benard' and Robertson" showed that sulfur absorbed on copper and that faceting was not observed.

Jan 1, 1967

By J. E. Flinn, S. A. Duran

The steady-state creep behavior of poly crystalline cad mi inn was studied over a temperature range of (1.56 to 0.94 Tm. Two distinct mechanisms were found to occur over this temperature range. They were described by: where and represerqt the minimum strain rates corresponding to the low- and high-temperature regions, respectirely. The two regions of constant acti11ation energy were connected by a transition region where the strain rate was controlled by both mechanisms acting in parallel. At temperatures below a transition temperature of about 0.7 Tm the agreement between the activation energy value for creep and that for self-diffiision suggests a rate-controlling mechanism of dislocation climb. For cadwzium, steady-state creep at temperatures above 0. 7 Tm appears to be controlled by another mechanism, perhaps involving the behavior of dislocation jogs. FRENKEL et al.1 studied the high-temperature creep of polycrystalline cadmium and reported an activation energy of 21 kcal per mole for the 0.5 Tm < T < 0.8 Tm range. Based on observations of creep rate at only two temperatures, a value of 22.1 kcal per mole was determined by Medbury. These two investigations were for the purpose of showing agreement between the activation energy for creep and that for self-diffusion, reported3 as 18.2 and 19.1 kcal per mole, respectively, for diffusion parallel and perpendicular to the hexagonal axis. Gilman4 investigated prismatic glide in single crystals of cadmium over a higher-temperature range of 0.72 to 0.93 Tm, and found an activation energy of 29 kcal per mole. He also reported5 an activation energy higher than that of self-diffusion for prismatic glide in zinc single crystals deformed at temperatures near the melting point. This value was in good agreement with those found for an equivalent temperature range by Flinn and Munson6 and by Tegart and sherby7 for polycrystalline zinc. These two independent studies also disclosed at lower temperatures another value of activation energy near that for self-diffusion. It would be expected from the creep results on zinc and single-crystal cadmium that creep studies on polycrystalline cadmium, extended to temperatures near the melting point, might yield an activation-energy value higher than the 22 kcal per mole value found in earlier studies. The purpose of this paper is to report the steady-creep behavior of polycrystalline cadmium over a temperature range of approximately 0.5 to 0.9 Tm EXPERIMENTAL METHOD The cadmium used in this study was obtained in the form of as-cast rods, 0.5 in. diam, through the courtesy of the Bunker Hill Mining Co. The material was of 99.995 pct purity, as determined by spectro-chemical analysis. The creep specimens, which were 0.250 in. diam by 0.400 in. long and annealed at 300°C for 45 min to produce a stable average grain diameter 0.25 mm, were tested in compression using an apparatus similar to that described by Sherby.8 The specimen temperature was controlled to within ±0.5°C with the help of appropriate constant-temperature baths. The applied stress was maintained within 1.0 pct of the desired value by the additions of lead shot at fixed strain increments. No barreling was observed over the strains encountered during testing. Isothermal creep tests9 were used in the study with only a few differential temperature tests10 run for comparison purposes. Steady-state creep data were obtained over a temperature range of 60 to 287°C (0.56 to 0.94 Tm) at five stress levels ranging from 28.1 to 140.6 kg per sq cm. RESULTS The minimum or steady-state creep rate may be described by an equation of the following form:" where i is the minimum strain rate, S is the structure factor, F is a stress function, Qc is the energy of activation, T is the absolute temperature, and R is the gas constant. The minimum strain rates obtained in this study for cadmium were recorded on a semilogarithm plot as a function of the reciprocal absolute temperatures for the various stress levels, as shown in Fig. 1. This figure shows a characteristic transitional behavior" with a parallel interaction of two mechanisms. It is obvious that the activation energies corresponding to the individual processes are insensitive to stress because the curves are parallel. The discrete activation-energies values for the low- and high-temperature regions for the various stress levels are reported in Table I, and were determined by the least-mean-square method. For the low-temperature region, an activation energy of 20.7 ± 0.6 kcal per mole was obtained, and for the

Jan 1, 1967

NAME AND OBJECT. SEC. 1. This Institute is incorporated under the Membership Corporation Law of the State of New York ; its corporate name is AMERICAN INSTITUTE OF MINING ENGINEERS; and its objects are such as are stated in its Certificate of Incorporation. ARTICLE II. MEMBERS. SEC. 1. The membership of the Institute shall comprise four classes, namely (1) Members ; (2) Honorary Members , (3) Associates , and (4) Honorary Associates Only Members and Associates residing within the United States of America, Republic of Mexico and Dominion of Canada shall be entitled to vote at the meetings of the Institute. SEC. 2 All Members, Honorary Members, Associates and Honorary Associates of the American Institute of Mining Engineers as the same existed on the day of the incorporation of this Institute, are Members, Honorary Members, Associates and Honorary Associates, respectively, of this Corporation SEC. 3. The following classes of persons shall be eligible for membership in the Institute, namely, as Members and Honorary Members, all professional mining engineers, geologists, metallurgists or chemists, and all persons practically engaged in mining, metallurgy or metallurgical engineering ; as Associates and Honorary Associates, all persons desirous of being connected with the Institute who, in the opinion of the Council, are suitable. SEC 4. Every candidate for election as a Member or Associate of the Institute must be proposed for election by at least three Members or Associates; must be approved by the Committee on Membership, as prescribed in the By-Laws ; and .must be elected by the Council. Not less than three-fourths of the votes cast shall be necessary to an election Every person so elected shall become a Member or Associate, as the case may be, upon payment of his first dues as herein-after prescribed Each candidate for Honorary Member or Honorary Associate, must be recommended by at least ten Members or Associates ; must be approved by the Council ; and must be elected by ballot at a meeting of the Board of Directors by the unanimous vote of all the Directors present ; provided, however, that the number of Honorary Members and Honorary Associates shall not at any time exceed twenty SEC. 5. If any person elected a Member or Associate does not, within sixty days after notice of his election, accept the same and pay his initiation fee and dues for the current year, his election may be cancelled at the discretion of the Council.

Jan 1, 1910

By I. Nilsson, G. Sundkvist, A. Danielsson

A spectrochemical method of slag analysis is descibed which utilizes fusion of the sample with a flux, then cooling and crushing to put all samples into a common form. The powder, is then fed onto adhesive tape and passed through a spark by means of a special device to provide very reproducible discharge conditions. Combined with a direct-reading optical emission instrument, this system provides speed and accuracy of antilysis heretofore unobtainable for. slag samples by any other method. THERE are many suggested methods for spectro-chemical analysis of slags. The most important are fusion-pellet methods and solution methods. In our company the fusion-pellet method has been used earlier, and is described by Lounamaa. W. H. Tingle and C. K. Matocha have made refinements of the pellet method.&apos; A Committee of the British Iron and Steel Research Association has investigated different methods of spectrochemical analysis of slags. Its purpose was to formulate a method which would give the complete analysis in 30 min with an accuracy of ±3 pct. The committee recommends a solution technique, which was thought to correspond best to their requirements. The method to be described is a fusion-tape method. The sample is isoformed by fusion and grinding. The powder is analyzed with the tape technique. The tape machine and some of its applications are described earlier.4&apos;5 The powder to be analyzed is continuously fed onto a moving adhesive tape, which passes through the spark gap. The sparks break through the tape and vaporize and excite the material to be analyzed. The most outstanding feature of the tape machine is its very high reproducibility. The concept of isoformation has been introduced earlier.= It means a pretreatment of the samples to make them uniform from the spectralanalytical point of view, i.e., cancelling systematic differences between the samples. The purpose of the isoformation is to reduce the influence of particle size, as well as chemical and mineral composition. Before describing the isoformation by fusion plus grinding, which is the purpose of this paper, a few words will be said about two other types of isoformations, i.e., grinding with buffer and ion exchange plus grinding as they have been considered during the application of the tape technique for slag analysis. Grinding with buffer might be a sufficient isoformation in some special cases, where the mineral composition is defined. The time of grinding must, however, be rather long, at least 5 to 10 min, even when using such an efficient mill as the Swing Mill from Messrs. Siebtechnik, Mühlheim, Germany. This type of isoformation is not recommended due to its limitations and due to the fact that the gain in time compared with the fusion technique is almost negligible. The principle of ion exchange plus grinding and some of its applications have been described.5 The following elements of interest in slag analysis can be determined in this way: Na, K, Cu, Mg, Ca, Ba, Zn, Pb, Al, Cr, Mn, Fe, Co, Ni. The very important element Si, however, cannot be analyzed with this method. Although the ion exchange isoformation for slag analysis cannot be looked upon as a routine method, it can be used for

Jan 1, 1962

By James D. Reilly

13.1-1. Introduction. COAL RESERVES OF THE UNITED STATES. Bituminous coal is the most abundant fossil fuel in America. With reserves of 1,660 billion tons and assumed recovery of 5070, there is more than 830 billion tons of recoverable coal--enough to assure ample supplies of energy for centuries. Looking at Fig. 13.1-1, coal is found in a majority of the states, including [ ]

Jan 1, 1968

By H. W. Smith, A. K. Bjerring

A nonlinear dynamic model for a flotation cell is developed, using a number of simplifying assumptions, the most important of which is that of essentially complete liberation in the feed material. Using this model, a complete dynamic model for a flotation circuit is developed and calibrated against steady- state process data. The dynamic response of the circuit to disturbances in input feed rate and composition is simulated, as is the response of a linearized and simplified model on which control design might be more easily based. Preliminary results indicate the practicability of the modeling technique. However, difficulties in matching steady-state operating conditions in one process stream, and the apparent importance of recycle streams as indicators of process operation, indicate that inclusion of at least one species of middling particle in the model should be considered.

Jan 1, 1969