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By W. C. Smith, P. J. Hickey

After a short historical background of the process evolution, this article descvibes present-day plant facilities and operating techniques utilized for high-purity bismuth production. The plant is one of the world's largest, with an annual output of some one million pounds of refined bismutlz. PREVIOUS papers1 written by staff members of Cerro de Pasco Corp. have referred briefly to the production of refined bismuth. Since the Corporation is one of the world's foremost producers of high-purity bismuth, a detailed description of the process for extracting the metal may be of general interest. Following a short historical background of the development of the actual process, this presentation will trace the progress of bismuth from its entry into the primary smelting circuits to its concentration in electrolytic lead cell slimes. Our facilities for the treatment of anode muds will be described and the extractive methods given in some detail, with particular emphasis on the techniques which result in the production of refined metal. HISTORICAL BACKGROUND Shortly after Cerro de Pasco began smelting operations at Oroya, Peru in 1922, it became apparent that the dust carried by copper converter gas contained appreciable amounts of bismuth. Although dust collection efficiency was poor prior to building of the 550-ft stack and installation of the central cottrells in 1938, a large stock of dust was accumulated during the intervening years, having the following approximate composition: Oz. per ton Ag - 11.0 Pct Sn — 0.5 Pct Pb - 49.0 Pct Zn - 6.5 Pct Bi - 2.0 Pct Insol. - 1.5 Pct Cu - 0.7 Pct Fe - 2.3 Pct Sb - 3.0 Pct S - 10.0 Pct As - 7.5 In the mid-1920's, experimental crucible melts of this dust with carbon indicated that most of the bismuth and silver, and some of the lead, could be reduced to a fairly clean bullion. Other products were a small amount of leady copper matte and a slag high in zinc, arsenic, antimony, and lead; this slag contained some tin but only small quantities of silver, bismuth, and copper. After the laboratory results had been confirmed by operation of a small reverberatory, a dust reduction furnace was constructed. The ±10 pct Bi-Pb bullion produced from this operation was stocked until 1930, when an Oroya-designed converter type furnace3 was installed for the elimination of arsenic, antimony, and some lead from the bullion. This process concentrated the bismuth from 10 to about 60 pct. By means of the bismuth process developed4 by W. C. Smith at East Chicago (1909-1914) and the discovery of a method5 for separation of lead from bismuth with chlorine gas in 1929, it became possible to begin production of refined bismuth. Unfortunately, bismuth deleaded with chlorine always contained residual chlorides, and the removal of the chlorides by caustic soda left a lead content of 0.02 to 0.04 pct. This final problem was solved6 by substitution of air-blowing for the caustic treatment, which effectively removed all excess chlorine and gave bismuth which was practically lead-free. In 1934, a pilot electrolytic lead refinery began operations at Oroya. Lead smelting was resumed in 1935 and two years later a 100-ton-per-day lead refinery was put into service. In conjunction with the latter, the present-day Anode Residue Plant was constructed. Until 1940, the plant treated both lead anode slimes and dust reduction bullion. The dust reduction furnace was shut down in that year, and all cottrell dusts (with the exception of the product from the arsenic cottrell) were mixed with pyrite and treated in a Wedge roaster to eliminate all possible arsenic. Calcine from this operation joined the sinter plant feed; hence the bismuth from the copper and lead circuits was collected in the lead bullion and subsequently in lead anode slimes from the electrolytic lead refinery. The latter source has been the only bismuth-bearing material of any consequence entering the Anode Residue Plant from late 1940 to the present. A copper refinery began operating in 1948, and the cell mud from this plant is mixed with lead slimes and processed through the same circuit, though only a small quantity of bismuth is present in electrolytic copper cell residues. BISMUTH INTAKE Present-day routes which are followed by the new bismuth feed from its entry into the primary smelting circuits to its arrival at the Anode Residue Plant are traced schematically in Fig. 1. As illus-

Jan 1, 1962

By W. D. Steele, S. D. Brady

THE Pittsburgh coal seam in West Virginia contains the largest coal reserves of any coal seam in that State and is, therefore, one of the most important seams, and attains mineable thickness and purity throughout that part of the seam extending from the Northern Panhandle to Monon¬galia Co. thence south and southwest across the state to Wayne Co. near Huntington. The Pittsburgh coal is also mineable in the Upper Potomac region but is now practically exhausted there. The total mineable areas of this coal amount to 2,165 sq miles and are estimated, by the West Virginia Geological Survey, to contain 13% billion net tons. The largest body of Pittsburgh coal outcrops on the western edge of West Virginia, along the Ohio river as far south as Moundsville, West Va., going under the river at that point and extending at various depths down the river as far as Wetzel Co. line where it thins out to such an extent that it has little practical value, and on the eastern edge this large body outcrops along the Monongahela River. The territory to be covered by this paper is the area known as the Northern. West Virginia District comprising Wetzel, Monongalia, Marion, Preston, Harrison, Doddridge, Taylor, Barbour, Upshur, Lewis, Gilmer, Braxton and Calhoun Counties, and is also known as Dist. 3 under the Bituminous Coal Act. This region was originally opened for commercial mining along and adjacent to the Monongahela River around 1852 when the Baltimore and Ohio Railroad was constructed to Fairmont. It has been extensively developed, first, in 188o (when the Monongahela River Railroad, now B. & O. R. R., was constructed) between Fairmont and Clarksburg, and later, in 1916, between Morgantown and Fairmont when the Monongahela Railway was constructed and placed in operation, this area furnishing the major portion of the production over the past years. With the mining out of a great deal of this territory adjacent to the Monongahela River considerable interest has been developed in the back acreage; and within the past few years a number of diamond core drill holes have been made in the back areas of Monongalia and Marion Counties. In this back area the oil and gas well drilling showed that the Pittsburgh coal seam was of mineable thickness and ranged in depth from 350 to 1,000 ft below the surface of the stream valleys but this drilling did not furnish any definite data as to its thickness and quality. ECONOMIC IMPORTANCE The Pittsburgh seam in Northern West Virginia is of primary importance as a coal resource not only because of its large reserves but because of its contributing a very large part of the coal used in this country for general steam uses. The Pittsburgh seam is a consistently thick seam, averaging 8 ft in thickness, with very easy grades underground, so it has always been

Jan 1, 1948

F. C. LANGENBERGW.*at 8ertoivn,M ass. (written cliscussiont).-I am inclined to the view that the change in physical properties encountered in the material with which the authors are working is due to the relief of internal strains. The statement, on page 1.098 of their paper, calling attention to the fact that this phenomenon disappeared when the material was rolled into 1 7/8 -in. square billets is of particular interest. It is certain that the internal strains set lip by cooling in a small billet of this size would be much less than those produced in a billet having a larger cross-section cooling under the same conditions. The statement that the physical properties of a given test bar were materially changed by standing has been brought to my attention in connection with the testing of gun forgings. I have made a number of observations on forgings produced at Watertown Arsenal to ascertain whether any change in ductility was produced by the aging of the test specimens. The results were always negative, but this can be explained by the fact that ii gun forging is generally a forging that has been quenched and subsequently drawn at a relatively high temperature.

Jan 10, 1919

By Alfred R. Powell

Late in 1944 a group of petroleum and coal technologists was organized in Washington under the sponsorship of the Petroleum Administration for War and the U. S. Bureau of Mines. This group, known as the Technical Oil Mission, was placed under the authority of the Technical Industrial Intelligence Committee of the Joint Chiefs of Staff, which was then promoting the organization of other missions to be sent to Germany to obtain technical information regarding various industries in that country. The objective of the Tehnical oil Mission was to obtain technical data on German production of synthetic oil from coal and all other commercial practices and research projects connected with the oil industry. The primary purpose was to obtain such data as were immediately essential to assist the war against Germany and Japan, with secondary emphasis on technical information that would assist American industry after the end of the war. since oil-production facilities in Germany and the occupied countries controlled by Germany were the top targets for strategic bombing, the Technical Oil Mission was the first group under the Technical Induslrial Intelligence Com,mittee to enter Germany. A few members of the group flew to London in February 1945 and the majority of the remainder followed in March. In London they were joined by an equal number of British investigators and the combined mission was then sent into Germany under the authority of the Combined Intelligence Objectives Subcommittee (CIOS). A summary of the more important information gained by this combined British and American mission is presented below. German Oil Production The oil available to Germany, both natural and synthetic, and including production from occupied countries, reached a peak in late 1943 and early 1944 Production at this time was at the rate of 1,200,000 metric tons Per month, equivalent to 100,000,000 bbl. per year, or about 7 per cent of the wartime production in the United States. Of this production, jo per cent was crude oil from Romania and Hungary, 12 Per cent was crude oil from Germany itself, including Austria, 9 per cent cumprised coal-carbonization products, that is, tar and light oil, and only the remaining 29 per cent was synthetic liquid fuel made from coal or tar. Synthetic liquid fuel made in Germany was equivalent therefore to less than 2 per cent of wartime production of crude oil in the United States. The success of the strategic bombing campaign against German oil-production facilities is demonstrated by the fact that by September 1944 the Ploesti fields of Romania and much of the syrlthetic oil production had been eliminated, so that the amount of oil available to the German war machine was only 25 per Cent of the peak qualltity mentioned above. By early 1945, when the combined British and American oil mission was entering

Jan 1, 1947

By Alfred R. Powell

Late in 1944 a group of petroleum and coal technologists was organized in Washington under the sponsorship of the Petroleum Administration for War and the U. S. Bureau of Mines. This group, known as the Technical Oil Mission, was placed under the authority of the Technical Industrial Intelligence Committee of the Joint Chiefs of Staff, which was then promoting the organization of other missions to be sent to Germany to obtain technical information regarding various industries in that country. The objective of the Tehnical oil Mission was to obtain technical data on German production of synthetic oil from coal and all other commercial practices and research projects connected with the oil industry. The primary purpose was to obtain such data as were immediately essential to assist the war against Germany and Japan, with secondary emphasis on technical information that would assist American industry after the end of the war. since oil-production facilities in Germany and the occupied countries controlled by Germany were the top targets for strategic bombing, the Technical Oil Mission was the first group under the Technical Induslrial Intelligence Com,mittee to enter Germany. A few members of the group flew to London in February 1945 and the majority of the remainder followed in March. In London they were joined by an equal number of British investigators and the combined mission was then sent into Germany under the authority of the Combined Intelligence Objectives Subcommittee (CIOS). A summary of the more important information gained by this combined British and American mission is presented below. German Oil Production The oil available to Germany, both natural and synthetic, and including production from occupied countries, reached a peak in late 1943 and early 1944 Production at this time was at the rate of 1,200,000 metric tons Per month, equivalent to 100,000,000 bbl. per year, or about 7 per cent of the wartime production in the United States. Of this production, jo per cent was crude oil from Romania and Hungary, 12 Per cent was crude oil from Germany itself, including Austria, 9 per cent cumprised coal-carbonization products, that is, tar and light oil, and only the remaining 29 per cent was synthetic liquid fuel made from coal or tar. Synthetic liquid fuel made in Germany was equivalent therefore to less than 2 per cent of wartime production of crude oil in the United States. The success of the strategic bombing campaign against German oil-production facilities is demonstrated by the fact that by September 1944 the Ploesti fields of Romania and much of the syrlthetic oil production had been eliminated, so that the amount of oil available to the German war machine was only 25 per Cent of the peak qualltity mentioned above. By early 1945, when the combined British and American oil mission was entering

Jan 1, 1947

By A. Kelly, S. Sato

Tensile tests have been performed on aluminum single crystals of 99.99 pct purity at 196°K. The resolved shear stress when the stress-strain curve becomes concave to the strain axis depends on orientation, being always higher for crystals with an initial orientation close to the sides of the unit triangle. Observations have been made, with the optical microscope, of the appearance of slip lines on polished surfaces of the crystals. Particular attention has been paid to the first appearance of cross-slip. It is confirmed that marked cross-slip is first seen when the stress-strain curve becomes concave to the strain axis. Measurements are reported of the lengths of the slip lines observed on top and side faces of the crystals at various stages of the deformation. The lengths of the slip lines vary inversely as the flow stress for all crystals, independent of crystal orientation. From measurements of the lengths and separations of the slip traces it is possible to estimate the number of dislocations which are annihilated at each cross-slip site. It is concluded that the annihilation of screw dislocations of opposite sign is the most important cross-slip process occurring. FRIEDEL1 recently pointed out that the stress-strain curve of many pure metals of face-centered-cubic structure can be considered as composed of three stages. Plastic flow commences with a region showing a small rate of hardening which is approximately linear. This has been called "easy glide*. It is followed by a region of more rapid hardening in which the slope of the curve is again approximately constant and this, in turn, is superseded by a final part of the curve which is concave to the strain axis. Following Diehl2 we may designate these regions as stages I, II, and III respectively. The onset of stage 111 occurs at lower stresses at higher temperatures. The appearance of the slip lines formed during these various stages has been described by a number of workers?-5* The object of the present work was to make detailed observations of the lengths and separations of slip lines for a number of crystals of different orientations deformed at the same temperature and strain rate. Although much previous work has been published on the deformation of aluminum single crystals the importance of measurements of these quantities has only recently been realized—they are essential for experimental tests of recent theories of work hardening.' 9 In aluminum, deformed at room temperature, stage 11 of the stress-strain curve is very weakly marked, as the stress for the onset of stage 111 is attained soon after the end of easy glide. In the present experiments it was decided to use a temperature lower than room temperature so that stage II of the curve was better developed. However, at temperatures as low as 90°K slip lines are not measured easily with the optical microscope.5 For this reason 1960k was chosen as a suitable temperature. Even at 1960k however, stage III of the curve commences at glide strains of 6 to 10 pct and hence

Jan 1, 1960

By C. L. Berrien

Before the present company was formed, in 1916, each group of mines comprising the old organizations made its detailed daily and monthly mine cost records along the lines used before the consolidation; that is, there was no attempt made to standardize and compare the stope costs of all mines. The general cost sheets for all mines, however, were standardized, and cumulative labor cost sheets were compiled in the general superintendent's office. At most of the mines, a daily record or distribution sheet for each working place was kept, showing the number of men, hours of drilling, hours of timbering, hours of tramming, cars of ore, cars of waste, sticks of powder and feet of fuse. This information was kept by each shift boss and entered on the distribution sheet by him or, at some mines, by a tram boss. The superintendent solved his own problems under the direction of the general superintendent, but without coming in touch with other superintendents, either through records or general conferences. Probably 95 per cent. of the stopes were square-set worked by day's pay; there were some back-filling and shrinkage stopes. Many of the development places, such as shaft sinking, station cutting, drifting and raises had always been run by contract. These contracts were given, for no definite period, at so much per linear foot and were measured monthly, or when completed, the men being paid monthly. In some cases, fairness to the employee was not maintained. On the whole, there was no standardization. There were no stope contracts, because of the objections of the Western Federation of Miners to general contracting in the mines. Changes in Stoping Methods Early in 1916, W. B. Daly, then general superintendent, and the author, then assistant general superintendent, visited the Southwest mining districts with the object of finding some improved mining

Jan 1, 1923

By C. L. Berrien

Before the present company was formed, in 1916, each group of mines comprising the old organizations made its detailed daily and monthly mine cost records along the lines used before the consolidation; that is, there was no attempt made to standardize and compare the stope costs of all mines. The general cost sheets for all mines, however, were standardized, and cumulative labor cost sheets were compiled in the general superintendent's office. At most of the mines, a daily record or distribution sheet for each working place was kept, showing the number of men, hours of drilling, hours of timbering, hours of tramming, cars of ore, cars of waste, sticks of powder and feet of fuse. This information was kept by each shift boss and entered on the distribution sheet by him or, at some mines, by a tram boss. The superintendent solved his own problems under the direction of the general superintendent, but without coming in touch with other superintendents, either through records or general conferences. Probably 95 per cent. of the stopes were square-set worked by day's pay; there were some back-filling and shrinkage stopes. Many of the development places, such as shaft sinking, station cutting, drifting and raises had always been run by contract. These contracts were given, for no definite period, at so much per linear foot and were measured monthly, or when completed, the men being paid monthly. In some cases, fairness to the employee was not maintained. On the whole, there was no standardization. There were no stope contracts, because of the objections of the Western Federation of Miners to general contracting in the mines. Changes in Stoping Methods Early in 1916, W. B. Daly, then general superintendent, and the author, then assistant general superintendent, visited the Southwest mining districts with the object of finding some improved mining

Jan 1, 1923

By W. F. Kieschnick, Eugene Harrison, W. J. McGuire

W. J. McGuire, et al, are to be commended for their undertaking of a mathematical solution of a very difficult problem. Unfortunately, however, a mathematical approach requires the application of several assumptions. These assumptions appear to be unrealistic and lead to answers which do not describe what actually happens when hydraulically fracturing oil and gas wells. Considering laboratory confirmation of breakdown phenomena, the authors appear to have tested their theories only on cement specimens and on samples of Austin limestone, much too small to provide any fracture system. This work resulted in the formation of vertical fractures. If the authors had tried similar experiments on thick walled cylinders made from almost any sandstone cores, they would have found that, using crude oil as the breakdown fluid, horizontal fractures would almost always occur, and at pressures much lower than any calculated. They would also find that by confining the fluid to within the bore (using oil base mud for example) on similar samples, the pressures required to burst the cylinders would be considerably higher and most of the fractures would be vertical. This breakdown pressure behavior has been duplicated in wells in Texas, Oklahoma, Kansas and in Wyoming. Considering field data the phenomena of different breakdown pressures for different breakdown techniques can be further illustrated. Most production and service personnel will agree that a breakdown can be more easily obtained if injection into a formation can be established prior to the occurrence of the breakdown. This is true whether the formation being treated is completed as open hole or as a perforated interval. This is clearly illustrated by a Lakota well in Wyoming, completed open hole at a total depth of 7,358 ft. An attempt to vertically fracture this well failed when a bottom hole pressure of 10,326 psi was insufficient to break down the formation. A non-penetrating type fluid (oil base mud) was in the well at the time the breakdown was tried." The oil base mud was then cleaned out of the well and replaced by a 30" API gravity crude oil. With this oil in the hole the formation breakdown was easily accomplished at a bottom hole pressure of 3,607 psi. This large difference in fracture pressures would be impossible according to the theories presented by McGuire, et al. The authors have used as an example the breakdown pressures experienced when acidizing Permian Basin wells. During acid treatments of limestone and dolomite the "breakdown" (drop-off in pressure) seldom occurs until some injection of acid has been accomplished. In these cases the breakdown is most likely to result from the chemical reaction of acid and rock in already existing vugs and fractures rather than from making a new fracture by hydraulic pressure. If this is true, then results in the Permian basin should not be used to validate the authors' calculations. *** AUTHORS' REPLY to ROSCOE C. CLARK and HENRY F. COFFER The purpose of our laboratory experiments in which thick-walled rock cylinders were hydraulically fractured was to determine the validity of the "thick pipe" formula for brittle materials, and not to predict nor demonstrate directly the orientation of field fractures. Our conclusions concerning field results resulted from calculations involving the "thick pipe" relationship as well as considerations of overburden stresses, rock strengths, and the geometry and dimensions of the field system. Clark suggests that had the models been more porous or contained weak bedding planes, horizontal fracturing would have occurred. This is undoubtedly true provided external stresses similar to those in the earth's crust are nor imposed. However, if we were going to design experiments to represent directly the field case we would impose the proper stresses on the models. It is generally recognized that the vertical compressive stress in the earth's crust arising from the weight of the overburden is approximately 1 psi/ft of depth. Then, as an example, even though a horizontal bedding plane has zero strength, the formation cannot be separated to form a horizontal fracture unless the hydraulic pressure exceeds the stress due to overburden. And in those cases in which the stress resisting vertical fracturing is significantly less than that resisting horizontal fracturing, vertical fractures should result, notwithstanding horizontal plane weaknesses. We agree that breakdown pressure will be less if the fracturing fluid penetrates the formation. In Appendix HI of our paper it is shown that leak-off reduces the pressure necessary to initiate either a horizontal or vertical fracture. It would be difficult to attempt to

Jan 1, 1955

By T. I Harkins, J. Brian Eby

This paper outlines the geophysical investigation of the area covering the Darrow salt dome, Louisiana. Surveys with the refraction seismograph and torsion balance failed to disclose the dome, but reflection dip shooting was successful and was confirmed by later drilling. Introduction The Darrow salt dome and oil field lies in western Ascension Parish, Louisiana, on the outside of a sharp bend and on the east bank of the Mississippi River. The dome occurs about 30 miles south of Baton Rouge and 80 miles northwest of New Orleans. Its geology, shape and structure have been ably described in detail by Carroll E. Cook1 and, except for the general features, will not be repeated here. The purpose of this paper is to record some of the interesting and pertinent geophysical data contributing to the discovery of the dome and eventually the oil field. The salt dome is circular in outline and comes to within about 4625 ft. of the surface. At this depth the diameter of the salt plug is approximately 4800 ft. The dome has only a thin cap rock of less than 75 ft. Some oil has been found and is being produced in Miocene sands above the cap rock, but most of the field's production comes from a narrow ring of wells around the east and south flanks of the dome. Producing horizons on the flank are found at 5670 to 5840 ft. in the Miocene and 6890 to 6985 ft., 7028 to 7060 ft. and 8260 to 8270 ft. in the Oligocene. The deepest well that has been drilled is the Humble Oil and Refining Company's Community B-5, on the south flank of the structure, which reached a depth of 10,013 feet. The size and shape of the field and the area of production are indicated on Fig. I. The line showing the area of production encloses all wells now producing and all abandoned producers, both on the top and flank of the dome. This line of production is shown on all subsequent geophysical maps as a direct means of comparing the early geophysics to later drilling development. Darrow dome occurs on the low, flat flood plain of the Mississippi River; it is protected from flood overflow by high artificial levees. The rich loamy soil supports a high degree of cultivation, principally sugar cane. Drainage is secured by many small canals and the water table of the area is at or near the surface. These particular conditions of topography, drainage and top soil greatly influenced the early geophysical picture, and the influence was always unfavorable. Surveys with Refraction Seishograph and Torsion Balance A reported oil show in a water well drew attention to the lands of the Belle Helene

Jan 1, 1943

By J. Brian Eby, T. I. Harkins

This paper outlines the geophysical investigation of the area covering the Darrow salt dome, Louisiana. Surveys with the refraction seismograph and torsion balance failed to disclose the dome, but reflection dip shooting was successful and was confirmed by later drilling. Introduction The Darrow salt dome and oil field lies in western Ascension Parish, Louisiana, on the outside of a sharp bend and on the east bank of the Mississippi River. The dome occurs about 30 miles south of Baton Rouge and 80 miles northwest of New Orleans. Its geology, shape and structure have been ably described in detail by Carroll E. Cook1 and, except for the general features, will not be repeated here. The purpose of this paper is to record some of the interesting and pertinent geophysical data contributing to the discovery of the dome and eventually the oil field. The salt dome is circular in outline and comes to within about 4625 ft. of the surface. At this depth the diameter of the salt plug is approximately 4800 ft. The dome has only a thin cap rock of less than 75 ft. Some oil has been found and is being produced in Miocene sands above the cap rock, but most of the field's production comes from a narrow ring of wells around the east and south flanks of the dome. Producing horizons on the flank are found at 5670 to 5840 ft. in the Miocene and 6890 to 6985 ft., 7028 to 7060 ft. and 8260 to 8270 ft. in the Oligocene. The deepest well that has been drilled is the Humble Oil and Refining Company's Community B-5, on the south flank of the structure, which reached a depth of 10,013 feet. The size and shape of the field and the area of production are indicated on Fig. I. The line showing the area of production encloses all wells now producing and all abandoned producers, both on the top and flank of the dome. This line of production is shown on all subsequent geophysical maps as a direct means of comparing the early geophysics to later drilling development. Darrow dome occurs on the low, flat flood plain of the Mississippi River; it is protected from flood overflow by high artificial levees. The rich loamy soil supports a high degree of cultivation, principally sugar cane. Drainage is secured by many small canals and the water table of the area is at or near the surface. These particular conditions of topography, drainage and top soil greatly influenced the early geophysical picture, and the influence was always unfavorable. Surveys with Refraction Seishograph and Torsion Balance A reported oil show in a water well drew attention to the lands of the Belle Helene

Jan 1, 1943

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

By J. F. Held

In a study of the influence of cold rolling on mechani cal properties of steel, it was found that the specific rolling procedure influenced crystallographic orientation. Properties developed by several rolling modes were determined and related to crystallographic orientation. Sanzples were cold-rolled various amounts on a laboratory mill. When palm oil was used as a lubricant, the crystallographic orientation was homogeneous throughout the thickness of the samples. Other samples were rolled without lubrication. Variations in intensity of the recrystallization texture components persisted throughout more than 50 pct of the volume of these samples. When the average plastic strain ratio, which is dependent upon crystallogvaphic orientation, was plotted as a function of percent reduction, a maximum was found at 40 pct in the samples which contained the observed texture variation. No maximum was found for the samples with the homogeneous texture distribution. Other mechanical properties, such as tensile strength and yield strength, were not influenced by the variation in crystallopaphic orientation. MECHANICAL properties of steel sheets depend, in general, upon the structural properties of the steel. For example, the Petch equation describes the relationship between yield strength and grain size. Other properties, such as hardness, vary with chemical composition. The plastic strain ratio, or R value, has been found to be dependent upon crystallographic orientation . In the course of investigating the effect of cold rolling on mechanical properties, it was found that a previously reported relationship between percent cold reduction and R value was not always observed. Published data had shown that the optimum cold reduction for best R values is 70 pct for aluminum killed steel.' However, by altering the rolling conditions, the optimum reduction can be shifted to much lower values, or it can be moved to very high values. This paper describes the rolling conditions that lead to shifting of the optimum cold reduction. The effect of rolling conditions on the various structure parameters and the resulting mechanical properties are evaluated. EXPERIMENTAL PROCEDURE Samples of three low-carbon aluminum killed steels were cold-rolled various amounts on a 9-in.-diam 2-high laboratory mill. Hot-mill thermal practice and steel chemistries are listed in Table I. Steel A was rolled with palm oil lubrication and heavy reductions on each pass; i.e., a total reduction of 75 pct was ac- complished with a maximum of five passes. Steel B was rolled without lubrication, and light reductions were given on each pass. After approximately 75 pct reduction, it was necessary to use a small amount of light oil to achieve any additional reduction in thickness. Following cold reduction, the samples were box-annealed at 1300°F for 10 hr. The heating rate between 800" and 1300°F was 50°F per hr, and the cooling rate following the soak period was 50°F per hr. Tensile specimens were machined from the annealed material and these were used to measure yield strength, tensile strength, and the plastic strain ratio (R value). Recrystallization textures were determined by an inverse pole figure technique.*'3 Integrated intensities of the (110), (002), (112), and (222) reflections were recorded for those planes lying parallel to the sheet surface. Examinations were made on both surfaces of each sample, and also at various levels beneath each surface to approximately 0.010 in. depth by etching techniques. RESULTS R Values. The R values obtained in steels A and B are shown as a function of percent cold reduction in Fig. 1. No optimum cold reduction was observed in steel A, rolled with palm oil lubrication. It is likely, however, that an optimum reduction would have occurred had higher reductions than 88 pct been employed. The optimum reduction in steel B occurred at 40 pct. The behavior in both of these steels is quite

Jan 1, 1968

By H. O. Jahns, R. A. Greenkorn, R. E. Haring, L. K. Shallenbarger

This paper is a study of the effects of heterogeneity on flow in an analog of porous media, the Hele-Shaw model. l-3 A set of experiments in heterogeneous Hele-Shaw models showed streamlines through and around heterogeneities of various sizes, shapes and levels. (A level, we define as the ratio between the transmissibility of the heterogeneity and that of the rest of the model.) The heterogeneities were restrictions or expansions of the flow stream analogous to variations in the transmissibility of porous media. The experimental data agreed well with numerical results and with an analytical solution, which we derived for a circular heterogeneity in an infinite field. This study considers the flow-stream distortion due to the shape, size and level of heterogeneities. Size and level are much more important than shape provided the heterogeneity is not long and narrow. Our analytical solution shows that a circular heterogeneity in a large field can be replaced by an equivalent circle of either zero or infinite permeability. The radius of the. equivalent circle is a simple function of size and level of the actual circle. INTRODUCTION With the availability of high-speed computers and numerical procedures to predict reservoir behavior, we are faced with an important question. How much information about the reservoir do we need to justify the cost of the computer in any given case? To answer this question, we have to know how various reservoir parameters affect flow behavior. Reservoir heterogeneity is one of these parameters. In this study, we used a simple, two-dimensional model of porous media, the hele-shaw model, to investigate the effect of heterogeneity on flow behavior. We restricted ourselves to linear, single-phase, steady-state flow in a rectangular field with a single heterogeneity at its center. The analogy between flow in Hele-Shaw models and in porous media is easily verified. Let us first consider a homogeneous Hele-Shaw model with constant plate separation h. (The Hele-Shaw model is constructed by placing two plates, usually glass, very close together and allowing liquid to flow between them. Streamlines are made visible by introducing colored fluid into the space between the plates at a number of points across the model.) We assume a cartesian coordinate system with its origin in the middle between the plates and the z axis directed perpendicular to the glass plates (Fig. 1). The fluid flow is always in a direction parallel to the glass plates and varies from a maximum value to zero in the very small distance from the middle (z = 0) to either plate (z = h/2). For slow motion of an incompressible fluid, neglecting inertia and body forces, we have the viscous flow equation: where p is the fluid pressure, p the viscosity, and v the velocity vector with components u, v and w in the x, y and z directions, respectively. In our rase. and the derivatives of 3 with respect to x and y are small as compared with the derivative in the z direction. Therefore, approximately, with Vp and v being two-dimensional vectors in the x-y plane. Two integrations with respect to z give

Jan 1, 1965

By F. C. Oliphant, George H. Fancher

Two samples of drilling mud from the Hastings oil field, Texas, were tested, and the solids in each were separated into small fractions of a limited range in particle size. The mineral composition of each fraction by X-ray analysis is reported, and the results are interpreted in relation to other measured quantities, such as the physical properties of the original samples and the density of the various fractions. It was found that only 7 to 8 per cent by weight of the solids was of colloidal dimensions and that neither of the samples contained montmorillonite but did contain illite. Considerable calcite was also found. These data should be useful to the geologist interested in the origin and history of sedimentary strata as well as to the petroleum engineer. Introduction The questions, What is good drilling mud? What constitutes bad drilling mud? are pertinent, because the proper use and control of drilling fluids has been a factor of great importance in the successful drilling and completion of oil wells since the days of Captain Lucas. Adequate control of the characteristics of drilling fluids has assumed greater significance comparatively recently because of the problems introduced by caving formations in deep wells, costly blowouts and impressive mud bills. Much is known about the solution of some of the problems but, despite extensive research directed toward a better understanding of the physical and chemical properties of clay suspensions, it is difficult to define precisely a drilling mud, and much more difficult to say what constitutes a good mud. It is generally believed that the smaller particles of a drilling mud greatly affect its physical properties. In fact, it is customary to blame the colloids in a mud for nearly everything that goes amiss, because colloidal properties have effects out of all usual proportion on viscosity, filtration rate and reaction to electrolytes. It is germane to know whether drilling muds possess colloids and if so, the quantity and kind. Source oF Samples Two drilling muds from the Hastings oil field, Brazoria County, Texas, were selected because it is generally agreed that in this oil field good natural muds made solely from formations penetrated by the drill can be used until the well is nearly ready for completion. Customary drilling procedure in this field is to spud in with water, set a protective string of pipe, drill to 2500 ft. and set the surface casing. Drilling is continued to 5500 ft. with no treatment of the drilling fluid other than addition of water to

Jan 1, 1943

By F. C. Oliphant, George H. Fancher

Two samples of drilling mud from the Hastings oil field, Texas, were tested, and the solids in each were separated into small fractions of a limited range in particle size. The mineral composition of each fraction by X-ray analysis is reported, and the results are interpreted in relation to other measured quantities, such as the physical properties of the original samples and the density of the various fractions. It was found that only 7 to 8 per cent by weight of the solids was of colloidal dimensions and that neither of the samples contained montmorillonite but did contain illite. Considerable calcite was also found. These data should be useful to the geologist interested in the origin and history of sedimentary strata as well as to the petroleum engineer. Introduction The questions, What is good drilling mud? What constitutes bad drilling mud? are pertinent, because the proper use and control of drilling fluids has been a factor of great importance in the successful drilling and completion of oil wells since the days of Captain Lucas. Adequate control of the characteristics of drilling fluids has assumed greater significance comparatively recently because of the problems introduced by caving formations in deep wells, costly blowouts and impressive mud bills. Much is known about the solution of some of the problems but, despite extensive research directed toward a better understanding of the physical and chemical properties of clay suspensions, it is difficult to define precisely a drilling mud, and much more difficult to say what constitutes a good mud. It is generally believed that the smaller particles of a drilling mud greatly affect its physical properties. In fact, it is customary to blame the colloids in a mud for nearly everything that goes amiss, because colloidal properties have effects out of all usual proportion on viscosity, filtration rate and reaction to electrolytes. It is germane to know whether drilling muds possess colloids and if so, the quantity and kind. Source oF Samples Two drilling muds from the Hastings oil field, Brazoria County, Texas, were selected because it is generally agreed that in this oil field good natural muds made solely from formations penetrated by the drill can be used until the well is nearly ready for completion. Customary drilling procedure in this field is to spud in with water, set a protective string of pipe, drill to 2500 ft. and set the surface casing. Drilling is continued to 5500 ft. with no treatment of the drilling fluid other than addition of water to

Jan 1, 1943

COLLECTIVE bargaining, hereto-fore loudly proclaimed as one of the stout timbers of the Republic, has passed from the picture. The coup de gr[a]ce was struck by the President of the United States when he ignored his vested legal prerogative and seized the steel industry by the dubious authority of, his "inherent powers." Autocratic judgment by a single official replaced arbitration by the steel industry and labor union. This is the outcome of a battle which has been bitterly waged for months in the hazy atmosphere created by well oiled propaganda machines. Prior to government intervention, there was no clear picture of the issues at stake. All parties concerned marshalled their accountants to conjure up figures proving their respective contentions. The results were fed into public relations departments for embellishment and dissemination. Thus, the public was asked to believe on one hand, that the steel worker, who is second only to the coal miner in hourly wages, was entitled to an increase in pay and other benefits. Nothing was said about the effect-of such an increase on the national economy. Industry in turn pointed to declining profits after taxes, but failed to mention the more than a billion dollars spent on plant expansion, in addition to the payment of substantial dividends for 1951. With the intervention of the administration, the immediate issue became clear to freedom-loving Americans. Is the executive branch of the government above the law, or is it supposed to uphold and carry out the .laws of Congress? The present administration forgot that it is a servant of the public and has become despotic. The American people must obliterate this dangerous precedent which has been set by the administration or accept the. ominous consequences of submission. Fortunately, the strongest weapon of the citizen-the ballot -still remains. When democratic procedure is restored, stabilization of the economy will continue to challenge us. This is the main public stake in the steel controversy. Only a solution based on bed-rock democracy will work. If the emergency is real, and we must assume that it is, this is the time for sacrifice. Industry and labor must meet without rancor to resolve wage contracts through collective bargaining. The government role, under emergency conditions, must be to objectively maintain wage, and price ceilings in the interest of stabilization. Political expediency cannot be permitted to' influence these controls. Politics and not the public weal have been the guide lines for too long. We are at the cross roads. By all sober judgment, this is the time for Americans to take a militant interest in their government today. Tomorrow will be too late.

Jan 1, 1952

By H. R. Banks

Pondering the action of a ball mill employed to carry on comminution from the product of fine crushing to the point where flotation, cyanidation or other concentrating methods are applicable, one wonders where this machine had its origin. When Henry Wadsworth Longfellow reiterated the observation of that older poet Von Logau, and wrote "Tho' the mills of God grind slowly, yet they grind exceeding small," he probably visualized the type of mill that was employed in medieval times for the production of flour, and can therefore not be considered as having gained admittance to the fraternity of millmen, on behalf of either poet. He does, however, make it quite clear that the efficiency of even these Mills of Destiny was low, and to that extent voices a characteristic of fine-grinding equipment that has been the bugbear of all metallurgical engineers. Principle of Ball Mill The principle of the ball mill probably is traceable to the action along the coast line of oceans or lakes, or in the mountain streams. Wave action on rocks and pebbles, close to the shore line, gives the potential energy to the grinding media, which, in their rolling and tossing, break down the sands, and the resultant "pulp" carried out from the shore is classified and settles out in sizes ranging downward to extremely he mesh. Surely, these are the real mills of God. If we allow our minds to dwell on the total tonnage that has been handled in this way, adding to the sands and clays at present in existence those enormous tonnages of metamorphosed sedimentaries we sense the vast quantity of rock that has been so reduced. Is it not likely, therefore, that the answer to the beginnings of pebble milling, and eventually ball milling, came through the perception of this natural mill by one of our engineering forebears? Methods of Grinding The relatively low return of mechanical input to a ball mill, in terms of useful work accomplished, has always intrigued me immensely. The potential energy absorbed by a ball raised to a high point in its path is apparently released with a very small return in useful work. Is the ball mill the most desirable means of he grinding, or is there some other method through which we can recover a reasonable amount of the energy input in terms of useful work? Some years ago, on his retirement, H. W. Hardinge was questioned as to his thoughts on the trend of fine-grinding equipment. As I recall, his prophecy at that time was that the most likely field for improvement in grinding media would be toward a charge of flat disks with some mechanical scheme to cause them to slide over each other. Undoubtedly, Mr. Hardinge went through the usual experience of the muller and bucking board, the customary introduction of the budding millman to his calling. I have often wondered, but have never got beyond the wondering stage, as to the

Jan 1, 1947

By H. R. Banks

Pondering the action of a ball mill employed to carry on comminution from the product of fine crushing to the point where flotation, cyanidation or other concentrating methods are applicable, one wonders where this machine had its origin. When Henry Wadsworth Longfellow reiterated the observation of that older poet Von Logau, and wrote "Tho' the mills of God grind slowly, yet they grind exceeding small," he probably visualized the type of mill that was employed in medieval times for the production of flour, and can therefore not be considered as having gained admittance to the fraternity of millmen, on behalf of either poet. He does, however, make it quite clear that the efficiency of even these Mills of Destiny was low, and to that extent voices a characteristic of fine-grinding equipment that has been the bugbear of all metallurgical engineers. Principle of Ball Mill The principle of the ball mill probably is traceable to the action along the coast line of oceans or lakes, or in the mountain streams. Wave action on rocks and pebbles, close to the shore line, gives the potential energy to the grinding media, which, in their rolling and tossing, break down the sands, and the resultant "pulp" carried out from the shore is classified and settles out in sizes ranging downward to extremely he mesh. Surely, these are the real mills of God. If we allow our minds to dwell on the total tonnage that has been handled in this way, adding to the sands and clays at present in existence those enormous tonnages of metamorphosed sedimentaries we sense the vast quantity of rock that has been so reduced. Is it not likely, therefore, that the answer to the beginnings of pebble milling, and eventually ball milling, came through the perception of this natural mill by one of our engineering forebears? Methods of Grinding The relatively low return of mechanical input to a ball mill, in terms of useful work accomplished, has always intrigued me immensely. The potential energy absorbed by a ball raised to a high point in its path is apparently released with a very small return in useful work. Is the ball mill the most desirable means of he grinding, or is there some other method through which we can recover a reasonable amount of the energy input in terms of useful work? Some years ago, on his retirement, H. W. Hardinge was questioned as to his thoughts on the trend of fine-grinding equipment. As I recall, his prophecy at that time was that the most likely field for improvement in grinding media would be toward a charge of flat disks with some mechanical scheme to cause them to slide over each other. Undoubtedly, Mr. Hardinge went through the usual experience of the muller and bucking board, the customary introduction of the budding millman to his calling. I have often wondered, but have never got beyond the wondering stage, as to the

Jan 1, 1947

By Orville R. Lyons

This paper presents a method whereby the amount of misplaced material and the difficulty of the separation can be used to compare coal cleaning equipment of all types, from effectiveness and capacity standpoints. The correlations presented do not include all types of equipment currently available, but the method can be used to evaluate any make or type of coal cleaning equipment, both old and new. THE relative performance of coal washing equipment, or the effectiveness with which any type or make of equipment removes impurities from coal, has been most difficult to evaluate in the past. The most widely used yardstick is the Frazer and Yancey efficiency formula developed in 1922,' but Yancey in a later article states that "washers treating coals of different density composition or operating at different densities of separation cannot be compared directly on the basis of this criterion."' Prior to and since 1922, a variety of other methods has been used for comparison purposes, including the distribution curve, the error area, and the "ecart probable" or probable error. Yancey and Geer in discussing these methods conclude, "Performance can be evaluated in a number of different ways, with the choice of the proper method to use being dictated by the objectives of the investigation and the data available."' It is true that performance can be evaluated in a variety of ways, but if the equipment is to be evaluated on an effectiveness basis, there should be only one universal comparison method. Varying methods have been used because one universal comparison method has not been found or developed. In the article previously quoted, Yancey and Geer state in clear terms the primary concept for a universal comparison method: "One of the simplest, and certainly one of the most obvious evaluations of washery performance is the quantity of sink material in the washed coal and the float material in the refuse. If the washery products are tested at the density at which the washing unit is operated, the sink in the washed coal and the float in the refuse represent material that has been misplaced." The quantity of misplaced material was used as a criterion of washery performance by Lincoln in 1913," by the United States Bureau of Mines in 1938,' by Hancock in 1947," and by the national French research agency Cerchar in recent years.' In 1950 Andersone proposed the use of this criterion as an efficiency value to replace the Frazer and Yancey formula. However, none of the above-mentioned investigators used the misplaced material concept in a manner that would provide universal coal-cleaning equipment comparisons. The Correlation Theory The ideal coal cleaning process would treat all sizes and would make a perfect separation at any given specific gravity. All material lower in density than the desired value would report in the coal product and all material higher in density would report in the refuse product. Unfortunately, no known cleaning process achieves this goal and there seems little likelihood that any process yet to be invented will do more than approach it. When coal is treated in volume under operating conditions, it is impossible to avoid mechanical entrapment, fluctuations in throughput and effective gravity of separation, and the creation of turbulent currents, even when a true heavy-liquid bath is used and the feed is closely sized and contains little intermediate gravity material. This being so, it is possible to appreciate the difficulties inherent in trying to obtain a perfect separation when treating a wide range of sizes and a feed containing high percentages of intermediate material, using turbulent currents to help create the effective separation gravity, under operating conditions which normally tend to be on the overload side. When coal is separated from refuse in any coal cleaning equipment, some refuse always reports to the coal and some coal to the refuse; the writer therefore assumed that there should be a relationship between the total amount of misplaced material produced by any given piece of equipment and the difficulty of separation as represented by the percentage of near gravity material in the feed. With small amounts of near gravity or k0.1 material in the feed there should be less misplacement of material than would occur with large amounts of near

Jan 1, 1953