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By J. Chipman, N. J. Grant, E. C. Roberts

An equilibrium study was made of the distribution of chromium and oxygen between liquid iron, containing less than 1 pct Cr, and simple slags of the CaO(MgO)-Si02-FeO-Cr& type in the temperature range 1526' to 1734OC. The effects of slag oxidation, temperature, and basicity were observed. IN spite of the fact that chromium is one of the most important alloying elements in steel, and exists in almost all steels as a significant residual element, little research has been done to determine its behavior in basic steelmaking processes. Considerably more work has been done under silica-saturated acid slag conditions. Korber and Oelsen,' Herasymenko,' and others have generally agreed that in acid steelmaking practice the chromium in the slag behaved as if it were present as the chrom-ous ion (CrO). Work by Hilty- ir, high chromium slags also indicated that chromium may exist as CrO. In basic slag systems no equilibrium data exist. Based on individual studies of basic open hearth and electric furnace practice, Bardenheuer," Rock-rohr,% nd HauckQ oncluded that: 1—chromium recovery increased with decreasing basicity, and 2— chromium recovery increased with increasing temperature, although the effect was small. In similar studies Yavioskii and Dzemyen' concluded that: 1— slag FeO is the most important variable, 2—the basicity of the slag has no effect on chromium recovery, and 3—slag viscosity is not high even when 20 pct Cr,O, is present. Lapitskii\ oncluded that chromium recovery improved as the basicity of the slag decreased and increased with increasing manganese in the metal. Regarding the effectiveness of CrZ08 as a base or acid in basic slags, both Kristofferseno and Trojer" reported that Cr,08 was an acidic component requiring neutralization as 2CaO-Cr,O,. Experimental Procedure The experimental apparatus and procedure used for the present research were similar in most details to those used by Winkler and Chipman" and were described in detail by them. A magnesia crucible was used, holding 60 to 80 lb of Armco iron which was decarburized with hydrogen to about 0.010 pct C. Since all the metal samples solidified without gas evolution, this carbon level was assumed not to be significant. Synthetic slags made by mixing pure oxides were used throughout the study. Temperatures were measured by means of calibrated W-Mo thermocouples and were checked by Pt-Pt-Rh thermocouples. The range of temperatures covered in this study was from 1526" to 1734°C. The chromium content of the iron was in the range 0.032 to 0.82 pct, although the bulk of the tests showed 0.04 to 0.2 pct. The slags were of the CaO(MgO)-SiO,-FeO-Cr,O, type in which the Cr,O, content was from about 2 to 20 pct, although most of the slags showed from about 2 to 10 pct. The FeO range was from about 10 to 65 pct. CaO and SiO, were in the range of about 5 to 45 pct each, yielding a rather wide range of basicity values. The first 12 heats were made without a sulphur addition, and with only 30 min allowed for slag-metal equilibrium to be reached. In previous research it had been shown that less than 30 min was adequate to achieve equilibrium in slags free of Cr2O8.11,14.15 A study of the present data indicated that some of the tests may not have reached equilibrium in this time; accordingly four additional heats were made in which at least 1 hr was permitted for equilibrium to be reached. For reaching

Jan 1, 1955

By T. H. Janes

NATURAL abrasives of some type are found in all countries of the world. In order of their hardness the principal natural abrasives are diamond, corundum, emery, and garnet, which are termed high grade, and the various forms of silica, including pumice, pumicite, ground feldspar, china clay and, most important, sandstone. The properties qualifying materials for use as abrasives are hardness, toughness, grain shape and size, character of fracture, and purity or uniformity. For manufacture of bonded grain abrasives such as grinding wheels, the stability of the abrasive and its bonding characteristics are also important. No single property is paramount for all uses. Extreme hardness and toughness are needed for some applications, as in diamonds for drill bits, while for other purposes the capacity of the abrasive to break down slowly under use and to develop fresh cutting edges is of greatest importance, as with garnet for sandpaper. In dentifrices, soaps, and metal polishes, of course, hardness and toughness are objectionable. First among the natural abrasives, industrial diamonds are essentially of three types: l—bort, which includes off-color, flawed, or broken fragments unsuitable for gems; 2—carbonado, or black diamond, a very hard and extremely tough aggregate of very small diamond crystals; and 3—ballas, a very hard, tough globular mass of diamond crystals radiating from a common center. Bort comes from all diamond-producing centers, carbonados only from Brazil, and ballas chiefly from Brazil, although a few of this last group come from South Africa. By far the largest producer of industrial diamonds is the Belgian Congo; the Gold Coast, Angola, the Union of South Africa, and Sierra Leone supply most of the remainder. There is no production in Canada, which imports $6 to $9 million worth of industrial diamonds annually. Industrial diamonds find innumerable uses in modern industry. They are used for diamond drill bits for the mining industry; in diamond dies for wire drawing; in diamond-tipped tools for truing abrasive wheels and for turning and boring hard rubber, fibers, and plastics; and in diamond-toothed saws for sawing stone, glass, and metals. High-speed tool steels, cemented carbides, and other hard, dense alloys can be cut, sharpened, or shaped efficiently only with diamond-tipped tools and diamond grinding wheels. .. Second only to the diamond in hardness is corundum, an impure form of the ruby and sapphire gems consisting of alumina and oxygen (Al²O³) with impurities such as silica and ferric oxide. Corundum generally crystallizes from magmas rich in alumina and deficient in silica, as in the nepheline syenites of eastern Ontario. Grain corundum is used in the manufacture of grinding wheels; very coarse grain is used in snagging wheels. Both types of wheels are employed in the metal trades, where the hardness of corundum, coupled with its characteristic fracturing into sharp cutting edges, makes it an ideal cutting tool. The finest corundum (flour grades) is used for fine grinding of glass and high-precision lenses. From 1900 to 1921 Canada was the world's leading producer of corundum. Following this period the deposits located in northern Transvaal of the Union of South Africa supplied more and more of the world's requirements, and since 1940 South Africa has provided almost the entire output, which has ranged between 2500 to 7000 tons a year during the last decade. Minor amounts have also been produced in Mozambique, India, and Nyassaland. Opportunities for Mining Corundum Corundum deposits in southeastern Ontario are of three types, which may be described as follows: 1—Scattered, irregularly-shaped deposits of coarse-grained corundum which could be mined by means of small pits. About 10 groups of such deposits are known. Although the tonnage of individual deposits of this type is not great, it has been estimated that several years' ore supply is available for a small tonnage operation. Deposits average about 9 pct corundum. 2—Large irregular deposits of coarse-grained corundum which would require mining by adit with possibly a scavenger operation on the remains of former surface deposits. The Craigmont deposit of this type produced about 20,000 tons of corundum concentrate during operations between 1900 and 1913. Most of the readily available surface ore was removed by operators during that time. Reserves of ore above road level have been estimated to average 7 pct corundum, but none of the so-called reserves have been blocked out, or even indicated, by diamond drilling. From 1944 to 1946, 2025 tons of

Jan 1, 1955

By J. J. Gilman

The dependence of ortho kink-band formation on crystal orientation, on temperature, and on the conditions at the ends of a specimen is described. Load-compression curves for crystals that kink are presented. The reversibility of ortho kinking is demonstrated, and motion of kink planes through crystals is shown. Finally, a phenomenological explanation of ortho kink-band formation is given. ORTHO compressive kink bands (Fig. la) were discovered for the case of metals by Orowan,1 and they have been discussed by Jillson2 and in some detail by Hess and Barrett." However, their history in nonmetallic crystals is considerably older. It is not known when they were first observed in mineral crystals, but descriptions of them may be found as early as 1885.* They were sometimes mistaken for twins.6 Mügge seems to have been first to realize their true nature and importance. He reviewed the knowledge of them for a wide variety of crystals: anhydrite, antimonite, kyanite, vivianite, gypsum, mica, graphite, molybdenite, barium bromide, cal-cite, sodium nitrate, and barite. Also, the "twins" observed by Bridgman7 in sapphire crystals resemble kink bands more than twins. The terms ortho and para kink bands have been coined in order to distinguish between two types of kink bands which seem to represent the same geometrical configurations, but which have different origins and sizes. Ortho kink bands are the usual type that form at low loads when zinc crystals are compressed parallel to the basal plane. Para kink bands form at much higher loads in highly deformed crystals. These terms refer to compression phenomena and are not to be confused with analogous tension phenomena such as tensile kink bands and deformation bands. Mügge described the geometry of ortho kink bands quite completely for kyanite crystals, Fig. lc. The geometry observed for cadmium by Orowan1 and for zinc by Hess and Barrett3 is very similar to that described by Mügge. (See Hess and Barrett for a complete discussion.) Mügge associated kinking with bending combined with basal slip. He pointed out that the kink angles

Jan 1, 1955

By R. C. Ellman

This report presents results of a series of tests on grindability of lignites and factors that influence grindability determination. All grindability tests in this investigation were made in the standard Hardgrove test apparatus. In addition to tests on standard samples of equilibrium moisture content, grindability determinations were made on air-and oven-dried samples of lignite representing the complete range of moisture content from normal bed moisture to nearly moisture-free conditions. Grindability index for all tests was calculated both by standard method and by an alternate or "corrected" method of calculation based on directly measured weight of fine-particle material produced in the grindability test. The second method of calculation allows more satisfactorily for loss of moisture during testing of high-moisture samples.

Jan 1, 1955

By A. J. Goss, M. Tanenbaum, W. G. Pfann

THE purification of two metals, antimony and tin, by zone refining is described, and a reciprocating method of passing molten zones through a straight ingot, which effects a considerable economy of time and apparatus, is discussed. Antimony has been used extensively as a doping agent in germanium and silicon. More recently, it has become important in the preparation of new semiconducting compounds such as InSb, GaSb, and AlSb. High purity is especially necessary in this latter use, since the antimony may comprise as much as 80 pct by weight of the compound. Antimony is generally available in a commercial form of about 99.8 pct purity. Column 1 of Table I is a typical emission spectra analysis of commercially available 99.8 pct antimony. Zone refining has been quite successful in increasing the purity of such samples. Columns 2 to 4 of Table I are analyses of an ingot of the antimony of column 1 after the passage of seven molten zones in an atmosphere of nitrogen. The ingot length was 9 1/2 in.; the mean zone length was 2 in.; convection was the only means of stirring. The column headings are sample locations in inches from the leading end of the ingot. The results illustrate both the merit and a limitation of zone refining. It is seen that four of the five impurities—nickel, arsenic, lead,

Jan 1, 1955

By A. F. Gregory

"AbstractA resumé of aerial radiation survey studies performed by and for Eldorado Mining and Refining, Limited, since 1943 is presented. Flight tests were initiated in 1947 and were followed .by intensified use and study of Geiger counters and other radiation detectors. Development of an aerial scintillation counter began in 1948, but •a sensitive large crystal unit was not available for exploration purposes until 1950. Modifications of this unit have been used in all subsequent surveys.For the Eldorado detector, several limiting conditions were established for successful radioactivity detection, the most important being that natural vein exposures can only be assuredly detected .at distances less than 150 feet. Sedimentary and pegmatitic radioactive occurrences can be detected at much greater distances. A helicopter investigation technique appears to •have •a useful prospecting potential.IntroductionAerial radiation surveys were first proposed in the early 1940's. However, it was not until 1949 that airborne detectors were extensively used in the search for radioactive minerals. Eldorado has flown about 50,000 miles of exploration flights, exclusive of tests, using a variety of •detectors and aircraft. Considerable data have •been gathered for .the evaluation of the several techniques employed. Much of the early work was performed with the co-operation of the National Research Council of Canada ( 1). More recent work was done in conjunction with the Commercial Products Division of Atomic Energy of Canada, Limited. The Development Department of this latter corporation designed and built the scintillation counter used in recent Eldorado surveys."

Jan 1, 1955

By A. Josefsson

The transition temperatures of 0.01 to 0.02 pct carbon steels are shown to be strongly influenced by cooling rate in the a range, quenching from A, causing a very low transition temperature even after strain aging. In a titanium-stabilized steel and in a steel with 0.05 pct C this effect is absent. NORMAL mild structural steels usually show a structure of more or less pure ferrite, as a matrix, in which cementite grains or pearlite are embedded. Of these components, ferrite is by far the most interesting one as far as ductility and brittle (cleavage) fracture are concerned. Obviously, pear-lite and carbide are by no means necessary for a cleavage crack to nucleate and grow in the ferrite, as steels with a very low carbon content (Armco iron with 0.02 pct C) have an impact transition temperature just as high as semikilled steels with 0.26 pct C.1 Although it has been argued that a very embrittling effect is to be expected from cementite, precipitated as continuous films along the ferrite grain boundaries,'. " the micrographic evidence for a direct causal connection between the brittleness and these films does not seem to be very convincing. On the other hand, it has been stated that cementite particles in ferrite are able to stop ferrite cracks.4,5 In any case, the properties of the ferrite itself seem to be of overwhelming importance to the ductility of steels, justifying a thorough study of steels consisting of ferrite of different compositions, but principally free from pearlite, which means a carbon content below 0.02 pct. Such investigations have been carried out using the impact transition temperature as a criterion of the tendency to brittle fracture and have given some rather unexpected results. One result is the profound influence of carbon on the transition temperature of the steel in normalized condition. If the carbon content is reduced from 0.02 to 0.015 pct and below, a nearly discontinuous decrease in transition temperature appears even with high percentages of such elements as phosphorus and nitrogen present. This will be reported elsewhere." The present paper deals with another effect of carbon upon transition

Jan 1, 1955

By Bruce F. Grant, Stefan F. Szasz

During 1947, a Sinclair research team was assigned to investigate thermal methods of oil recovery. The assignment was recommended by a survey of possible research approaches to increase the amount of oil that ultimately can be recovered from oil producing reservoirs. The use of heat to stimulate oil production rates by the melting of paraffin deposited in well bores can be traced back to within one or two decades of the drilling of the Drake well. The application of heat on a larger scale has been discussed by generations of oil producers. Shortly after the turn of the century, one intrepid operator is reported to have injected steam into a Pennsylvania property. After a few weeks, he apparently became discouraged and terminated his experiment. Subsequently, the literature contains references to several well-developed techniques for supplying heat to a producing well bore to melt paraffin or to reduce the viscosity of oil contained in the formation immediately around the well bore.1.?.3.4 Some early references discuss procedures to furnish heat to the reservoir,5,6 with the injection well as the heat source, thus obligating the process to maintain the entire rock mass at a temperature above that at which the desired improvement in oil recovery would occur. Another approach to reservoir heating was reported by a group of Russian technologists in 1935.7,8,9 They definitely demonstrated that combustion can occur within the porous structure of an oil-bearing sandstone. Their field experiments, however, relied less on combustion within the rock than on heat furnished by combustion of oil supplied to the injection well bore. Ignition of the air-oil mixtures in the well bore was found very difficult, and the field tests were carried on for only short periods of time. Publication of the Russian work spurred at least one independent operator in this country to try firing an air-gas injection well, on for only short periods of time. Publication of the Russian work spurred at least one independent operator in this country to try firing an air-gas injection well. The Brundred Oil Corp. reportedly obtained combustion in the sand immediately around the injection well bore, but the experiment was abandoned because of interference with normal production schedules. Injection capacity of the experimental well was greatly reduced by firing. The well was reshot and pieces of sand showing partial fusing of the quartz matrix were recovered. To the authors' knowledge no other field experiments utilizing combustion techniques for formation heating were undertaken prior to 1948, although the patent literature evidences continued interest in formation heating."'," CONCEPT OF COMBUSTION-SUPPORTED HEAT WAVE The references cited were in agreement that heat applied to a reservoir would increase recovery, but there

Jan 1, 1955

By W. H. Ashby, R. W. Cassingham, C. R. Blomberg, J. B. Justins

The Brookhaven field is one of several Basal Tuscaloosa reservoirs located in south-central Mississippi. It is a standstone reservoir, of erratic deposition and with several faults, having an approximate subsea depth of 9,800 ft. A large variation in permeability exists with a weighted average being 256 md. Estimated average interstitial water saturation is 45 per cent. The undersaturated reservoir fluid exhibits marked differences in physical properties with measured saturation pressures ranging from 733 to 2,255 psi. Early rapid decline in reservoir pressure caused the operating interests to unitize the field and initiate a program of pressure maintenance by gas injection. At the time gas injection was commenced, the reservoir pressure had fallen to nearly half of the original pressure with only 4.5 Per cent of the original oil in place produced. The reservoir pressure has since been maintained at approximately 2,750 psig, and cumulative production to date is 17 per cent of original oil in place. An analysis of field performance during gas injection is presented in detail. The program of pressure maintenance by gas injection is considered to be a success, since the expected ultimate recovery has been increased and the current production rate is in excess of 2 per cent of original oil in place per year. Performance has been better, anticipated ultimate recovery is larger, and total production costs are lower than for a similar Basal Tuscaloosa reservoir nearby, even though that field appears to have a more effective natural water drive. INTRODUCTION The history of the Brookhaven Unit is a testimonial for unitization and for the application of engineering techniques in the operation of an oil field. The operating and royalty interests in this field have mutually benefited from their early recognition of the need for unitization and pressure maintenance and from the forthright manner in which these were accomplished. The tangible benefits accruing to the participants in the Unit are: (1) income from gasoline plant products, (2) reduced lifting and operating costs from those of competitive operation, (3) maintenance of high levels of current income by mitigation of the inevitable decline in production rates inherent to natural depletion, (4) an increase in ultimate recovery of about 40 per cent over natural depletion operations. This paper should properly be considered a progress report; however, the performance of the field after five years of pressure maintenance clearly indicates that the ultimate success of the project is assured. LOCATION AND GEOLOGY The Brookhaven field is located in south-central Mississippi, about six miles from the town of Brookhaven. Production at Brookhaven

Jan 1, 1955

Cadmium occurs in the Broken Hill Lode essentially as a camouflaged element, substituting diadochically for zinc in the sphalerite.Analyses of a series of zinc concentrate flotation products, prepared from samples of ore taken at intervals throughout the developed lengths of the several orebodies forming the lode, have revealed a pattern in the distribution of cadmium relative to zinc. This pattern appears to reflect the temperature and order of deposition of the several orebodies, and the direction of movement of the mineralizing solutions.INTRODUCTIONThis investigation into the distribution of cadmium in the several orebodies of the Broken Hill lode was undertaken by the Mineragraphic Section. of C.S.I.R.O. in conjunction with the Broken Hill Geological Research Committee, as part of a study of Broken Hill mineralization.It arose from the examination of cadmium and zinc assays supplied by Mr. T. A. Read, Chief Metallurgist of the Broken Hill South Ltd.; of experimental zinc concentrates prepared from localized samples of the No, 2 and No. 3 orebodies in the Broken Hill South Mine. These assays suggested that the two orebodies were characterized by distinctive ZnjCd ratios.In view of the possible sigmficanc'e of such a difference, comparable data were sought from each of the other mines. The necessary samples of ore were collected by the geological staffs of the several mines. The preparation of separate zinc concentrates and lead concentrates from these samples, and their assaying, was conducted by Mr. Evan Hardy, for the North Broken Hill Mine, and its assodated leases, and by Mr. D., Swan, under the direction of Dr. J. C. Nixon, for the Zinc Corporation and New Broken Hill Consolidated Mines. Additional tests on the Broken Hill South Mine were made by Mr. C. W. Reilly, under the direction of Mr. T. A. Read. The samples were...

Jan 1, 1955

By J. J. Wallace

1. The Pittsburgh is the most important bed in Greene County from the standpoint of present production and recoverable reserves. 2. Known measured and indicated reserves in all beds, based on a minimum thickness of 14 inches and 1,800 short tons per acre-foot of coal in place, are estimated at 6,011 million short tons as of January 1, 1954. Of this total, 5,967 million short tons is in beds 28 inches and more thick. Areas in some beds were omitted from the estimate because available data relative to the bed characteristics are too meager to make an estimate that conforms with the definitions of measured and indicated coal adopted for this study. Should future drilling or development prove reserves in these areas, such reserves should be added to the total estimated reserves.

Jan 1, 1955

By S. Gilbert, G. R. Bailey

A further evaluation of the bomb-sampling method for determining the oxygen content of liquid steel is presented. The results of this study and their close agreement with the results of an earlier evaluation confirm the conclusion that the bomb-sampling method is valid for obtaining representative samples for the determination of the oxygen content of a liquid steel bath. WHAT constitutes the most desirable procedure for obtaining a sample suitable for determining the oxygen content of a liquid steel bath has been a controversial subject for several years. In 1952 Huff, Bailey, and Richards' described a modification of the bomb-sampling technique originated by McCutcheon and Rautio.' In both the modified and original techniques, a small cast-iron or steel mold containing aluminum wire and appropriately covered is inserted into the furnace, coated with slag, and then plunged into the metal bath. Upon entering the metal, the cover melts and a sample of the steel bath enters the mold. The data presented by Huff, Bailey, and Richards' indicated that reproducible samples could be obtained by their method. Furthermore, the oxygen analyses from samples obtained by their method agreed better with those from controlled laboratory experiments than did analyses from samples obtained by methods previously suggested for sampling large liquid-metal baths. Most techniques, other than bomb-sampling, require that a sample of liquid steel be removed from the furnace in a well slagged spoon and poured into an iron mold containing aluminum or into a massive copper mold for rapid chilling. Pouring in this manner requires that the sample pass through the air. The controversy, then, is somewhat as follows: Proponents of the spoon-sampling method and similar dip-and-pour methods feel that the introduction of a cold steel mold into a molten steel bath may result in a localized boiling condition that may deplete the steel of oxygen to a significant degree in the area where the bomb is introduced. Conceivably this boil could cause results that are, on the average, too low and nonrepresentative of the bath composition. On the other hand, samples that are spooned and then poured through the air may also be nonrepresentative because of oxidation by the atmosphere. The restrictions imposed in sampling with a spoon are much more stringent than those imposed when sampling with the bomb-type mold within the furnace. The spoon sample must be taken in a well slagged spoon, a requirement that depends on the condition of the slag in the furnace. Also, the samples must be poured as quickly as possible, without shaking the spoon and without allowing slag to enter the mold. The necessity of fulfill-

Jan 1, 1955

By R. G. Nelson

This report covers investigations of the Bureau of Mines for the period of June 15, 1952, to June 15, 1953, on a research project for the Materials Laboratory, Wright Patterson Air Force Base, Dayton, Ohio. The primary purpose of this investigation was to make high-purity chromium-base alloys having room-temperature ductility and high-temperature strength. The Nonferrous Metals Branch of the Bureau of Mines, Albany, Oreg., has, during the past 7 years, developed on a laboratory scale a hydrogen treatment method for making high-purity chromium that can be fabricated into thin sheet and wire. This material can be bent at room temperature. The object of this investigation was to use this material to develop improved chromium-rich alloys for high-temperature uses.

Jan 1, 1955

Jan 1, 1955

By K. G. Wikle, W. W. Beaver

The factors which control the rate of dissolution of pure gold in cyanide solution were studied both directly and through measurement of solution the current-potential curves for the anodic and cathodic portions of the reaction. The mechanism of dissolution is probably electrochemical the reaction in nature, and the rate is determined by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on their relative concentrations. The significance of the results and the effects of impurities are considered. ALTHOUGH the dissolution of gold in aerated cyanide solutions has been used as an industrial process for treatment of gold ores since the late nineteenth century, the factors which determine the rate of the reaction have never been identified unambiguously. Studies of the rate of dissolution by Maclaurin,1 White,2 Christy,3 Beyers,4 Thompson,6 and others are contradictory in their conclusions; some claiming that diffusion of the reactants to the gold. surface controls the rate, and others that the chemical reaction is inherently slow and related to high activation energy for the reaction. Christy3 and 'Thompson" both suggest that the reaction is electrochemical in nature and that the dissolution of gold proceeds at local anodic regions while the oxygen is reduced at cathodic regions on the gold surface. Although their studies are ingenious and do indicate an electrochemical reaction under the conditions of study, their experiments were of limited nature and failed to identify the rate-controlling process in the system. The importance from an industrial viewpoint of a knowledge of the mechanism and rate-controlling factors in gold dissolution can be illustrated as follows: If the rate is controlled by a slow chemical reaction rather than by diffusion of the reactants, then an increased temperature should have a marked accelerating effect; agitation of the slurry should have no effect on rate: and increased concentration of reactants should cause acceleration of the rate. If the rate is controlled by the diffusion of one or the other of the reactants to the gold surface, then increased agitation should increase the rate; increased temperature will increase the rate, but not as much as for the case of a slow chemical reaction; increased concentration of the reactant which is diffusion limited will increase the rate; and the concentration of other reactants should be without effect on the rate. It may be concluded that for design of a commercial process for gold leaching, the rate-controlling factors of the reaction should be understood so that an intelligent choice of the conditions of agitation, temperature, and reactant concentration may be made. The experiments described here lead to the unambiguous conclusion that in a system of pure gold and a pure aerated cyanide solution the rate of dissolution is controlled either by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on the relative concentrations of each. There is also ample, but not conclusive, evidence that the mechanism of the reaction is identical to that of electrochemical corrosion. The practical significance of these conclusions will be discussed later in the paper. Experimental The experimental method used in this work was to employ an electrolytic cell which performed the overall gold-dissolution reaction, and to study the anodic and cathodic reactions of this cell as to their nature and the rate-controlling factors. Simple experiments on the rate of dissolution and the potential of the dissolving specimen also were performed under conditions of agitation, temperature, and concentration identical to those used in the electrode studies. Analysis of the electrode studies by well established theories of electrochemical corrosion were made, and the results were found to bear a one-to-one relation with actual rate and potential measurements. Electrode Studies: The Anodic Reaction: The gold specimen used for all of the electrode studies and the rate determination consisted of a sheet of 99.99 + pct Au wrapped around a lucite rod and sealed at the edges with plastic cement, thus forming a cylinder of gold of known and constant area (8.0 sq cm). The lucite rod was threaded into a brass spindle which could be rotated at speeds of 100, 300, and 500 rpm. For the electrode studies electrical contact between the gold cylinder and the brass spindle was made by means of a gold strip covered with plastic. The anodic dissolution of gold was studied by immersing the electrode in a solution containing known concentrations of KCN and KAu(CN)2 but free of oxygen, and by passing an anodic current through the gold electrode. The pH of the solution was maintained between 10.5 to 11.0 in these and all other tests by addition of KOH. The pH was measured before and after each test by means of a glass-elec-

Jan 1, 1955

By J. D. Forrester, Erich Sarapuu, T. C. Cheasley

John G. Tripp-—The concept of converting fuel deposits in-situ to useful forms of energy and chemical raw materials has important possibilities as a means of stretching out our fuel resources. The authors have worked in this field for years and in fact are among the pioneers in developing in-situ techniques based on underground electrocarbonization. Their efforts have aroused great interest in this subject and their contributions will undoubtedly gain even more significance as time goes on. The 4 to 5 billion tons of petroleum are proved reserves, that is, they are completely defined and could be produced economically with present methods of recovery. Reserves of coal, tar sands, and oil shale shown in Table I are not equivalent to proved reserves as the term is used in the oil industry. Incidentally, the 4.3 billion tons of oil shown in the tabulation is equal to about 28 billion barrels of oil and, therefore, presumably does not include reserves of natural gas liquids estimated at about 5 billion barrels. The relative comparisons would be more complete if these liquids together with the reserves of natural gas were included in the tabulation. It is stated in the report that production costs of the order of 10c per million Btu's could be expected from a large industrial electrocarbonization installation. The authors state that the operation probably could be operated successfully and at a profit. I would like to express my view that for the operation to be profitable extremely favorable conditions would have to prevail. For example, the coal seam would have to be thick and close to the surface in order to minimize drilling costs; the deposit should be dry and so situated that there would be little, if any, inflow of ground water; and the seam would have to be relatively gas tight to avoid excessive gas leakage. Notwithstanding the tremendous strides that have already been made, it is my hope that the authors plan to continue their development work. Experiments on underground electrolinking and initial carbonization at Gorgas, Ala., indicate a need for improved control over the operation. Subsequent examination of the underground system at Gorgas has shown that the gasification zone did not always follow a direct path between the electrodes. Undoubtedly the control of the in-situ thermal processes can be improved by further development work. With respect to the electrocarbonization of oil shale it may be well to point out that the cost of mining oil shale is estimated to be 50c to 60c per ton. These are low mining costs as compared to coal. Thus it would appear that there is less economic incentive for applying in-situ thermal methods to oil shale than there is for applying these methods to coal. As is the case with in-situ methods for petroleum, the product from the shale having the most economic interest would be liquid oil rather than gas. The authors point out that for distances up to several hundred miles it is cheaper to transmit energy as electricity than it is to ship energy as coal. This is a very important point, and with coal shipping rates rising periodically, it could prove increasingly important in the future. I believe that the authors deserve great credit for their outstanding work on underground electrocarbonization. The knowledge resulting from their efforts is of great value to our fuels technology. James L. Elder—The experimental work conducted by the authors on the electrolinking-carbonization of carbonaceous materials in situ is of great interest. The method is of great importance in the development

Jan 1, 1955

By D. T. Van Zandt

IN the late 1920's rotary drills began to replace the churn drills in the petroleum industry, but until the middle 1940's the churn drill was the only widely accepted means of drilling large-diameter blastholes for quarry operations. The Calcite plant of the Michigan Limestone Div., U. S. Steel Corp., was one of the first to experiment with rotary drills for quarry blasthole drilling, and the first to employ compressed air on a fully rotary rig to cool the bit and raise the cuttings to the collar of the blasthole. The Calcite plant operates a limestone quarry near Rogers City, Mich., in the northern part of the lower Michigan peninsula. The formation quarried, a portion of the middle Devonian series, is the Dundee limestone, which is uniform, seldom massive, and characterized by definite bedding planes. The dip is southeast, 40 ft to the mile. Quarry faces vary from 20 to 116 ft in height. Vertical blastholes are used entirely, from three to five rows of holes being drilled parallel to the working face, spaced 18 ft apart with 18-ft burden and drilled 6 to 8 ft below shovel grade. Quarry operations coincide with the navigation season on the Great Lakes, as the bulk of the stone is transported by lake carrier. The normal operating season runs from April to December, the remaining time being devoted to stripping operations and plant and equipment maintenance. In the followirig discussion drilling rates mentioned refer to overall drilling time and include all operations such as moving from hole to hole, penetration and extraction of tools, and routine maintenance. Time consumed by such factors as power delays and major machine repair is not included in drilling time unless otherwise stated. Figures cover only operations at this one plant in the formation mentioned. Needless to say, a very different set of figures could be obtained in a different formation. However, the comparison of footage obtained with churn drills and rotary rigs in this particular formation has been used as an indication of what might be the expected performance of rotary rigs in other formations. Prior to 1950 the bulk of the blasthole drilling at the Calcite plant was done by electrically powered churn drills. Both crawler and wheel-mounted rigs were used. These machines, which mounted a 22-ft drill stem of 4½ in. diam and a spudding type of bit 2 to 4 ft long, drilled a hole of 5 ?-in. diam. Average drilling rate of these rigs in the Rogers City formation was 8 % ft per hr. In 1946 one of the first rotary blasthole drills offered to the quarry industry was put into use on an experimental basis. This machine, known as the Sullivan Model 56 blasthole drill, Fig. 1, was on 16-in. crawler pads and electrically powered at 440 v. The drill bit, a Hughes Tri-Cone roller bit of 5?-in. diam, Type OSC, was threaded into the end of the 4-in. square hollow drill rod or stem. These drill rods were 20 ft long with female threads on one end and male on the other to allow for addition of the desired number of rods for drilling holes of various depth. Rods were handled by a single drum hoist geared to the main drive motor and racked by a 30-ft derrick or mast when not in use. The cable from the hoist drum fed through a crown block on the top of the derrick back to the water swivel mounted in the top end of the drill stem in use. This cable remained attached during drilling operations and was used to hoist the tool string from the hole. Down pressure was applied to the tool string by means of a pair of 4-in. diam hydraulic cylinders acting on the drill chuck holding the drill rod. The first chuck consisted of flat jaws which gripped the flat sides of the stem. These jaws were controlled by set screws forcing them into contact with the drill stem. As these set screws had to be loosened and tightened by hand with each stroke of the hydraulic feed cylinders, there was great delay. For this reason the semi-automatic chuck was developed which automatically gripped the stem on the downward stroke but released for retraction of the hydraulic feed cylinders. Rotation was imparted to the tool string by a rotary table acting on the chuck and geared to the main drive motor through a separate gear train and clutch. A positive displacement water pump, mounted on the drill, fed water through a system of pipes and hose into the water swivel mounted on the top of the drill rod and through the rod and bit, washing the drill cuttings to the collar of the hole. Where water was scarce, provision was made to settle out the cuttings coming from the collar of the hole and re-use the water. Where water was abundant the stream coming from the hole was wasted. Drilling rate with this machine was about 20 ft per hr and bit life 1600 ft of hole. While this rate was more than twice that obtained with the churn drills employed, the problem of water supply and drill cuttings disposal rendered the machine impractical from an operating standpoint. Consequently it was used only in that part of the operation for which water was easily supplied, when the character of the formation made it least difficult to wash cuttings away from the collar of the hole. In October 1949 it was suggested that drill cuttings be removed by compressed air, long used for this purpose on pneumatic drills, and collected at the collar by suction. Thereafter, the water pump on the Sullivan 56 was replaced by a 500-cfm air compressor and a trial run made. Air pressure at

Jan 1, 1955

By M. T. Simnad, G. Derge, I. George

Measurements of current efficiency on iron-silicate slags in iron crucibles showed that conduction is about 10 pct ionic in slags with less than 10 pct silica and about 90 pct ionic in slags with more than 34 pct silica, increasing linearly in the intermediate range. The balance of the conduction is electronic in character. Silicate ions are discharged at the anode with the evolution of gaseous oxygen. Transport experiments show that the ionic current is carried almost entirely by ferrous ions, which may be assigned a transport number of one. THERE has been increased evidence in recent years that the constitution of liquid-oxide systems (slags) is ionic.1-3 The principal studies designed to establish the structure of liquid slags have been by electrochemical methods', " and conductivity measurements1,6,7 which also have indicated the presence of semiconduction in several silicate systems1,4-0 and in pure iron oxide.' It is well known that many slag-forming metallic oxides have an ionic lattice type in the solid state, and their properties are determined to a large extent by the lattice defects and ion sizes. As Richardson8 as pointed out, the detailed models of liquid slags cannot be found on thermodynamic data only but "must rest on a proper foundation of compatible structural and thermodynamic knowledge, combined by statistical mechanics." A careful thermodynamic study of the iron-silicate slags has been carried out by Schuhmann with Ensio9 and with Michal.10 They obtained experimental data relating equilibrium CO2: CO ratios to slag composition and made thermodynamic calculations of the activities of FeO and SiO, and of the partial molal heats of solution of FeO and SiO2 in the slags. It was found that the activity-composition relationships deviate considerably from those to be expected from an ideal binary solution of FeO and SiO2. However, the partial molal heat of solution of FeO into the slags was estimated to be zero. Their experimental results were correlated with the constitution diagram for FeO-SiO2 of Bowen and Schairer,11 with the results of Darken and Gurry" on the Fe-O system, and with the work of Darken"' on the Fe-Si-O system. All these studies were found to be consistent with one another. The variation of the mechanism of conduction with composition in the liquid iron-oxide-silica system in the range from pure iron oxide to silica saturation (42 pct SiO2) in iron crucibles was reported in a preliminary note." The current efficiency, or conformance to Faraday's law, showed some ionic conductance at all compositions, the proportion increasing with the concentration of silica. The current-efficiency experiments since have been extended. Furthermore, transport-number measurements have been completed in silica-saturated iron silicates to determine the nature of the conducting ions. Experimental Current Efficiency in Liquid Iron Oxide and Iron Silicates using Iron Anodes: This study was carried out by passing direct current through slags in the range from pure iron oxide to iron oxide saturated with silica (42 pct silica), using pure iron rods as anodes and the iron container as the cathode. A copper coulometer was included in the circuit to indicate the quantity of current passed during electrolysis. Assuming that the cation involved is Fe-+, the theoretical quantity of iron lost from the anode according to Faraday's law may be calculated and when compared with the actual loss observed, gives an indication of the extent to which Faraday's law has been obeyed. It also gives an indication of the presence and extent of ionic conduction in the melt. Preparation of the Slags: About 100 g of chemically pure Fe,O, powder is placed in an iron pot which is heated by induction until the contents liquefy. In this way, FeO is produced according to the reaction Fe2O3 + Fe = 3 FeO. More Fe2O3 or SiO, powder is added and, when a sufficient quantity of molten slag is obtained, the induction unit is turned off, the pot withdrawn, and the molten slag poured on to an iron plate. Homogenization and Electrolysis of the Slag: Apparatus—After considerable development, the setup illustrated in Fig. 1 proved to be quite satisfactory. A is an Armco iron cylinder, 1 in. ID and 1/8 in. wall, consisting of three sections placed one on top of the other. The bottom section is a pot about 5 in. long with a small hole drilled in its bottom to allow withdrawal of gases during evacuation of the apparatus. The middle section is 6 in. long and consists of a pot which serves as the slag container, while the top section is a hollow-cylinder continuation of the slag-container pot. The height of this latter section is about 5 in., giving an overall length of approximately 16 in. The iron cylinder is constructed in this way for ease of fabrication, the individual sections becoming welded together after the

Jan 1, 1955

By D. Turnbull, R. E. Cech

EXPERIMENTAL studies of precipitation of iron from solid solution in copper by Gordon and Cohen 1, Bitter and Kaufmann 2 and Smith 3 revealed that the precipitate particles were initially paramagnetic but could be changed to a ferromagnetic

Jan 1, 1955

By C. O. Bundranl, Peter Dehlinger, W. H. Browne

Brief laboratory investigations are described which attempt to determine optimum .sand concentrations in gel-sand and oil-sand1 well-treatments. The investigations apply to the case where sand acts as a propping agent in formation fractures. Both analytically and experimentally it is demonstrated that optimum sand concentrations can be defined. It is difficult to translate laboratory results to field treatments, however, since the relative distribution of sand and fluid in fractures may not be the same as injected. This is because fluid may penetrate the furtherest narrow portions of fractures, which would not pass sand. Optimum concentration of a monolayer of Ottawa sand in fractures of 0.025-in. width at the usual range of pressures encountered in treatments appears to be about 95 to 2 lb/gal. of gel. An investigation of abrasion of rock-walls by sand in treatments, described in the Appendix, shows that such abrasion is not probable in significant amounts. INTRODUCTION Experience in the Spraberry formation of West Texas, as well as in other formations, has shown that. sand is a necessary and vital part of gel-sand and oil-sand treatments. Many observers of treatments have also concluded that there seems to be an optimum range of sand concentration for these injections. Brief laboratory investigations were made at Battelle Memorial Institute to study flow in fractures with different sand concen- trations. To investigate the existence and range of optimum concentrations in the laboratory, however, necessitates knowledge of the mechanism by which the sand aids in increasing subsequent production. The action of sand in fractures is usually thought to be either that of a propping agent, thus providing a greater effective formation permeability; that of an abrasive in eroding fill material in fractures; or that of an abrasive eroding rock-wall irregularities along fracture surfaces. Investigations described in the Appendix show that sand does not appear to erode rock-wall materials appreciably. In a subsequent paper it is reasoned, at least for the Spraberry formation of West Texas, that the primary action of sand is not in removing fill materials in fractures. In this formation, and probably others, too, the main effect of sand appears to be that of a propping agent. Both analytical and experimental investigations were made for the case of a monolayer of sand acting as a propper, in which sand concentrations were determined that would, after treatment, permit flow of the maximum quantities of oil from the formation into a well. If too few sand grains are injected into fractures in which the bottom hole pressure has decreased appreciably below the original formation pressure, the confining pressure in the formation may become relatively large, thus compress the rock-walls around the sand grains, essentially close fractures, and so decrease the subsequent flow of oil. Similarly, if too much sand is used, the flow of oil will he impeded by the volume of sand present. THEORY Although an analytical approach to determining optimum sand concentrations involves gross assumptions.

Jan 1, 1955