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By William J. Campbell

The possibility of chemical analysis by identification of characteristic X-ray spectral lines was first suggested by H. C. J. Moseley in 1913.3/ For a given spectral series it was found that the frequency of the characteristic radiation was proportional to the square of the atomic number of the excited atom. Siegbahn and his coworkers improved the instrumentation and accurately determined the wavelengths of the characteristic spectra for most of the elements .4/ In fluorescent X-ray spectroscopy, the characteristic X-rays of atoms are emitted or fluoresced upon absorption of primary or incident X-rays of shorter wave-lengths (higher energies). The K spectral lines are used for elements of atomic numbers 13 to about 63, and the L series for those above atomic number 50. Whether the K or L lines are used for elements 50-63 depends upon the type of instrumentation available. The laboratory at the Eastern Experiment Station of the Bureau of Mines, College Park, Md., uses the K lines up to atomic number 57 and the L lines for thong elements of higher atomic number.

Jan 1, 1955

By Owen F. Jensen

CONSTRUCTION of a ground-water supply includes many operations, which do not end with completion of facilities. Evaluations must be made of the quality of water in various areas and the history of production. Following an analysis of geologic, hydrologic, and chemical data there must be an exploratory drilling program and a study of resulting information. When the well is completed a continuous survey of operating records and basic data is necessary, since designs for future wells are varied as more data becomes available for those already completed. As the following discussion must be limited to a single undertaking, the customary procedure will be outlined for development and construction of a ground-water supply in which more than three wells are involved. Parts of this procedure are applicable for all ground-water supplies. Three possible sites were selected for construction of a paper mill. The problem was that the industry daily required approximately 15 million gallons of water of the best quality available; however, if water of the best quality were not available in the desired amount, water of a poorer quality could be used up to half the required amount, about 7 million gallons. In the preliminary survey approximately 1500 to 2000 square miles were covered for each site. Collected data consisted of several hundred electric logs of oil and gas wells; reports by the U. S. Geological Survey on ground-water resources of localities in and near the area; unpublished records of several hundred water wells including chemical analyses of the water produced and drillers' logs of the wells; records of periodic water-level measurements made in observation wells by the USGS; topographic maps drawn up by USGS and by army engineers; and highway and county road maps. A preliminary report based on study and evaluation of these data was presented to the client, recommending the site with the most favorable and economical ground-water conditions. The study indicated that water of the quality and quantity desired could be developed. In this particular area there were indications that the aquifer could be separated into two zones con- taining water of different chemical character. This chemical character varied somewhat with area, but principally with depth, a factor which later proved an economic advantage in design of the well field. After studying the preliminary report, the client weighed other economic factors as well as ground-water advantages and selected a plant site. Authority was given to proceed with detailed study of the chosen area. Evaluation of preliminary data concerning the area indicated that it should be supplemented with additional information derived from actual exploratory drilling and testing. A flexible plan of exploratory drilling was devised so that data obtained as each test hole was drilled could be correlated with existing data and additional test holes could be located and drilled accordingly. Specific data to be obtained from each test hole were: samples of all formations penetrated; the driller's descriptive log of formations; electric logging surveys; one or more samples of water from selected water-bearing formations; temperature; and water levels and their recovery after periods of production. The area studied in such detail was approximately 400 square miles. Choice of location for the original test holes was based on the preliminary study. The pattern for these test holes was designed to require a minimum number of holes and to allow for interpolation of data between two, three, and four holes. Geologic, hydrologic, and chemical data gathered after completion of the first four test holes showed that the north section was the most desirable in the area, which was then reduced from the original 400 square miles to about 150 square miles for more detailed and intensive study. On the basis of findings from the current test a tentative well field was laid out and a drilling program devised. One test hole was located on the actual plant site and later developed into a small pilot production well equipped with a deep well turbine pump. Water from this well was used for general construction requirements. Another test hole drilled near the pilot production well and adjacent to the proposed route of the well-collection system was used during the pumping test of the pilot production well to determine the degree of interference. From the data thus obtained, calculations were made to determine the coefficients of transmissibility and storage. Three additional holes

Jan 1, 1955

By R. Schuhmann, J. Th. Overbeek, P. L. De Bruyn

THE technique of concentrating valuable minerals from lean ores by flotation depends upon the creation of a finite contact angle at the three-phase contact, mineral-water-air. If the mineral is completely wetted by the water phase, contact angle zero, there is no tendency for air bubbles to attach themselves to the mineral. However, when the contact angle is finite, the surface free energy of the system, water-air bubble-mineral particle, can be diminished by contact between the bubble and the particle, and if not too heavy the mineral will be levitated in the froth. With a few exceptions, all clean minerals are completely wetted by pure water. Thus the art of flotation consists in adding substances to the water to make a finite contact angle with the mineral to be floated, but to leave the other minerals with a zero contact angle. The contact angle concept and experimental measurements of contact angles have played important roles in flotation research for several decades.'-" Nevertheless, there remain unanswered some basic questions as to the scientific significance of the contact angle and the nature of the processes by which flotation reagents affect contact angles. The contact angle is a complex quantity because the properties of three different phases, or rather of three different interfaces, control its magnitude. Considering the interfaces close to the region of ternary contact to be plane, the relation among the contact angle and the three binary interfacial tensions is easily derived. The condition for equilibrium among the three surface tensions, Fig. 1, or the requirement of minimum total surface free energy leads to Young's equation, Eq. I: ysa — ysl = yLA cos 0 [1] According to this equation, the contact angle has one well-defined value. Actually it is found in many experiments that the value of the contact angle depends on whether the air is replacing liquid over the solid (receding angle) or the liquid is replacing air (advancing angle). The receding angle is always the smaller of the two.4 Two explanations have been offered for this experimental fact. According to some investigators,5-8 roughness of the surface causes apparent contact angles that are different for the receding and the advancing cases although the actual local contact angle may be completely determined by Eq. 1. The other explanation involves the hypothesis that the solid-air interface after the liquid has just receded is different from the same interface when no liquid has previously covered it.1,4 Adsorption of constituents of the air or liquid might play a role here. In this discussion the difference between advancing and receding contact angle will be neglected and plane surfaces where Eq. 1 describes the situation will be considered. But there is still a fundamental obstacle to the application of Young's equation. The surface tension of the liquid (rla) can easily be determined, but the two surface tensions of the solid (rsa and ySL) cannot be measured directly. Eq. 1, however, is not without value. By contact angle measurements it is possible to establish how ysl — ysl varies with the addition of solutes to the liquid phase. Also, Eq. 1 affords a convenient starting point for calculating net forces and energy changes involved in the process of bubble-particle attachment.1,2 . If for the moment surface tension of the liquid (yLa) is considered a constant, an increase in ysa — ysL, will tend to decrease the contact angle. A decrease in ySA — ysl, corresponds to an increase of the contact angle. In cases where ySA — ySL > yLa the contact angle is zero; it will only reach finite values when ysa — ysa has been decreased below YLA. Thus on the basis of Young's equation and contact angle measurements alone, it can be learned how flotation reagents affect the difference Ysa — ysl, but no conclusions can be drawn as to the effects of reagents on the individual surface tensions ysa, and ysL, not even as to signs or directions of the surface tension changes resulting from reagent additions. A quantitative relationship between the surface tension or interfacial tension and the adsorption occurring at a surface or an interface is given by the Gibbs equation, which for constant temperature and pressure reads dy = — 2 T, du, [2] where dy is the infinitesimal change in surface tension accompanying a change in chemical potential

Jan 1, 1955

By P. Raffinot, M. Rey, V. Formanek, G. Sitia

Six years of laboratory study, followed by three years of mill operation treating more than 10,000 tons of ore, have established the flotation of oxidized zinc ores with fatty amines as an efficient process. Recently the method has been applied with success to partially oxidized sulphide ores. In this paper the authors give an account of their research and the milling results obtained in Sardinia since 1951. CONCENTRATION of oxidized copper and lead ores by flotation has been practiced for 30 years, but flotation of oxidized zinc ores has remained unsolved until a few years ago. This problem is, however, of great importance in mining districts where large tonnages of oxidized zinc ores exist in underground mines or in dumps. Some sulphide ores also possess a degree of oxidation high enough to justify recovery of oxide zinc minerals. Various attempts have been made to float the zinc carbonate, smithsonite. It is well known' that smithsonite can be collected with fatty acids, but as the predominant gangue constituents, limestone and dolomite. are floatable with the same reagents, fatty acids are difficult to use. Gaudin has shown,' on mixture of pure minerals, that smithsonite can be floated with higher xanthates, or better, with higher mercaptans. Another procedure, briefly mentioned by Davis," consists in sulphidizing the ore, activating the zinc carbonate with copper sulphate, and floating with ordinary xanthates. This process was attempted in the writers' laboratory in 1946, but results were erratic. It has since been taken up by Italian engineers and is in operation on certain types of ores. Two other research projects should be mentioned. In 1942 Erlenmeyer and others' floated synthetic mixtures of smithsonite and gangue minerals with hydroxyquinoline, an analytical reagent for zinc. On the other hand, Bunge, Fine, and Legsdin published in 19465 Some interesting results obtained on Missouri oxidized zinc ores. With sodium oleate as a collector and a combination of sodium hydroxide, sodium silicate, and citric acid as a limestone depressor, they secured, after four cleaning operations, a good grade of concentrate. With many ores this reagent combination lacks adequate selectivity. In 1939 M. Rey initiated a program of research on this important problem. Work was pursued first at the School of Mines in Liége, Belgium"' and later in Paris in the laboratories of Société Miniére et Mbtallurgique de Penarroya and Société Minerais et Métaux. Reagents used in the beginning were higher xanthates and mercaptans, later fatty amines. Sulphidization with sodium sulphide was found necessary. These conditions make possible the flotation of zinc carbonate and zinc silicate. Two milling plants were put in operation in Sardinia in 1950 and several others are now contemplated." ' It should be mentioned that unknown to the present writers McKenna, Lessels, and Peterson were

Jan 1, 1955

By R. L. Beatty

IN INDUSTRIAL and domestic daily life carbon monoxide is the most frequently encountered toxic gas. hazardous concentrations of carbon monoxide may be present in the vicinity of many industrial operations, such as metallurgical processes, coke ovens, and fuel- and synthesis-gas producers, and may be encountered in confined spaces, such as dwellings, garages, workshops, vehicular tunnels, and mining operations, in connection with the use of heaters, boilers, internal-combustion engines, after blasting operations, and after fires and explosions. Evaluation and control of the health and safety hazard caused by carbon monoxide depend primarily on the analytical detection of the presence of carbon monoxide and determination of its concentration in air and in various gaseous mixtures. The choice of method of analysis in any particular situation depends on such factors as required accuracy, range of concentration involved, convenience, speed of analysis required, quantity of sample available, qualitative composition of sample or atmosphere to be analyzed, and possible effects of interfering gases. Some of the methods described require only adequate understanding of operational techniques, whereas others require thorough appreciation and skill in applying the principles involved. The instruments and analytical procedures commonly used for detecting and determining carbon monoxide are described in detail, and reference is made to more specialized methods:

Jan 1, 1955

By M. E. Wadsworth, R. C. Peterson, W. M. Fassell

The temperature and pressure dependence of the reaction of tantalum in oxygen were investigated from 500° to 1000°C at pressures from 10 mm Hg to 600 psi total oxygen pressure. Tantalum was found to oxidize linearly under the above conditions. Three distinct regions of temperature dependence were found with different energies of activation. From 500° to 600°C the rate of oxidation of tantalum was found to be essentially independent of the oxygen pressure at the pressure investigated. The oxidation rate increases rapidly with an increase in pressure from 600' to 800°C. The dependence of the oxidation rate on the bulk concentration may be expressed by V = k'?, where k' is the specific rate constant and ?=k1Co2/(l + K1Co2), where k, is the equilibrium constant for the adsorption of oxygen on tantalum. ONLY a limited amount of data has been presented in the literature on the oxidation behavior of tantalum metal. Some values of its oxidation rate were reported in the Corroston Handbook' and by McAdams and Geil.' The first extensive investigation of tantalum was the work of Gulbransen and Andrews." They determined the reaction rates of tantalum in O2 and N2. Their results indicate that this metal follows the parabolic law in the temperature range of 250" to 450°C in O2 at pressures of 7.6 cm Hg with an activation energy of 27,400 cal per mol. In nitrogen, the metal follows the parabolic law from 500" to 800°C at 7.6 cm pressure. All experimental determinations were of 2 hr or less duration and deviations from the parabolic rate conceivably could occur at longer times. A spectrophotometric study of the oxidation of tantalum by Waber, Sturdy, Wise, and Tipton' indicated good agreement between this method and the microbalance technique. The experiments were conducted in air from 220" to 350°C. The metal was found to follow the logarithmic law up to 320°C and the parabolic law at higher temperatures. The activation energies in the logarithmic region were reported as 12.57 kcal per mol and 12.0 kcal per mol, respectively, for the microgravimetric and spectrophotometric methods. In the parabolic region the activation energy was found to be 27.2 kcal per mol, in good agreement with the value of Gulbransen and Andrews." The present paper is concerned with the behavior of tantalum from 500" to 1000°C in oxygen at pressures ranging from 1/2 to 40.8 atm pressure. Earlier preliminary data by McKewan5,6 indicated the following facts concerning the behavior of tantalum: 1—At temperatures from 500" to 600°C, the metal followed the linear law. 2—At 575°C the rate of oxidation was found to increase with O2 pressure. 3—The Arrhenius plot in this temperature region was nonlinear. The nonlinearity of the Arrhenius plot was indicative of a more complex behavior than originally suspected for this metal.

Jan 1, 1955

By R. L. Orr, O. D. Sherby, J. E. Dorn

Creep data for pure metals at temperatures above those at which rapid recovery occurs (above about 0.45 the melting temperature) are correlatable by means of the equations and These correlations were applied successfully to data for aluminum, iron, nickel, copper, zinc, platinum, gold, and lead as well as for simple alloys. For a given metal, AH is a constant about equal to the activation energy for self-diffusion. THE early recognition that creep is stimulated by thermal activation prompted numerous investigators', ' to apply the same laws that are valid for the viscous behavior of liquids to analyses of creep data. To a good first approximation these laws are summarized by the equation were i is the creep rate; T, the absolute temperature; R, the gas constant in cal per degree per mol; T, the applied stress; AH, the activation energy in cal per mol; S', a constant dependent on the entropy of activation, the frequency of activation, and the contribution of each activation to the strain; and B', a constant dependent upon the size of the flow unit that is activated. Although Eq. 1 describes the flow of viscous fluids very accurately, its application to the creep of solids has been disappointing. Two reasons for the failure of Eq. 1 for creep are now known: First, the decelerating creep rates during primary creep demand that the internal structures of the metals are changing and that these changes might be reflected by changes in one or more of the three creep parameters S', AH, and B'. Consequently when the conventional methods of evaluating these parameters are employed by comparing the secondary creep rates at a series of temperatures and at a series of stresses, the true effects of temperature and stress are masked because of simultaneous changes in one or more of the creep parameters. Second, as will be illustrated more fully later, three distinctly different types of investigations have shown that the stress term for high temperature creep enters the analysis as and not as t/T. This rather unexpected result points sharply to a significant fundamental difference between the mechanisms for the viscous behavior of fluids and the high temperature creep of metals. More recent extensive investigations",'4 on the creep of high purity aluminum and several of its dilute a solid solutions have shown that where E is the total creep strain; temperature compensated time = for a constant temperature test; t, is the initial stress in a constant load test or the constant true stress in a constant stress test;" and t is the duration of test. • Eq. 2 is valid for either constant stress or constant load tests; but the total creep curve is difierent (i.e. the function, f, is differentl for each test. The fundamental origin of the validity of Eq. 2 is thought to arise from some equivalence of substructures in constant load creep tests at equal values of 0 or E. Both X-ray and metallographic examination revealed that practically identical lattice distortions and subgrain sizes are obtained for the same creep strain under the same load over wide ranges of test temperature.' Furthermore the room temperature tensile properties following equal creep strains at different temperatures under constant loads were also identical, illustrating that identical substructures were indeed obtained.' " A second type of correlation was obtained by differentiating Eq. 2 with respect to time, giving For the secondary creep rate, denoted by i,, But Eq. 2 reveals that 0, is a function of a, alone because the secondary creep rate in a given constant load test is always reached at a fixed value E,". Therefore where is the function that was introduced a number of years ago by Zener and Hollomon." Eq. 4 is not only valid for creep but will permit correlations between constant load creep and tensile data where e, is the rate of tensile straining and (TC is the engineering ultimate tensile strength.

Jan 1, 1955

By L. S. Richardson, N. J. Grant

REACTIONS of oxygen and nitrogen at low pressures with titanium have recently been studied by a number of investigators.1-3 Gulbransen and Andrew' noted that the reaction with nitrogen followed the parabolic rate law whereas the reaction with oxygen deviated slightly from this law in the temperature range 300° to 800°C. In the work reported here, commercial titanium (75 A) was used as the test material. Cylinders 2.5 in. long and 0.25 in. in diameter were machined from heavier bar stock. The test pieces were given a metallographic finish, immersed for 30 min in cold concentrated HC1, washed in water, then acetone, and dried with lint-free cloth. Reaction rates were determined in a modified Sieverts type apparatus by measuring the decrease in gas pressure of the reacting gas contained in a constant volume. The amount of gas added could be measured in a calibrated gas burette to an accuracy of 0.01 mm. During the course of a run the temperature never varied by more than 10°C and then only for brief moments. After placing the specimen in the furnace, the system was first evacuated for 12 hr at room temperature, and then flushed with purified argon five times, adsorbed gases being discharged during this period from the glass system with a high frequency spark coil. The flushing and discharging were repeated at 400°C. This rather involved procedure was found necessary after a number of trial runs indicated extraneous effects traceable to the system. Reaction periods up to 2 hr were used, at initial gas pressures of 0.2 to 0.5 atm. Experimental Results Fig. 1 shows the decrease in oxygen pressure for tests at 0.5 atm at various temperatures as a function of the square root of the time. Deviations from linearity are minor and the parabolic rate law is obeyed. Fig. 2 shows the same plot for the nitrogen reaction. A definite deviation from linearity is noted; however, it is probable that the higher initial rates are caused by the presence of small amounts of oxygen contamination, the initial faster rate changing to the slower rate after about 5 to 10 min. Calculations of the rate constants were made on the basis of the latter portion of the curves. The parabolic rate law constants calculated from these curves are shown for oxygen and nitrogen in Fig. 3. In spite of some scatter the average curves are quite definite. Changes in gas pressure of the order of 20 pct did not result in a measurable change in the rate law constants. The activation energy for the oxygen reaction was calculated to be 47,400 cal per mol (above 700°C), which is not in agreement with the value quoted by Gulbransen and Andrew' for lower temperatures, their value being 26,000 cal below 600°C. The activation energy for the nitrogen reaction was calculated to be 45,400 cal per mol above about

Jan 1, 1955

In 1953, Dr. N. H. Fisher of the Bureau of Mineral Resources, acting on behalf of the Society of Economic Geologists, which is considering the sponsoring of a uniform system of nomenclature for ore reserves, enquired from the Australasian Institute of Mining and Metallurgy whether it had ever considered this subject and particularly whether it had ever set up any standard definitions or specifications with regard to ore reserves.As this had not been done, but was thought to be desirable, the Council of the Institute appointed a Committee consisting of H. H. Dunkin, Associate, Professor of Mining Engineering, University of Melbourne (Convenor), E. A. Rudd, Professor of Economic Geology, University of Adelaide, I. N. Campbell, Chief Geologist of Western Mining Corporation; and the writer to consider and report on this supject.In December 1953, the Committee submitted its first report to the council and this report (reproduced here as an Appendix) was widely circulated among member companies, and engineers, with an invitation to comment on the proposal. A large number of, replies was received and studied.After studying the replies the Committee issued a second report in part as follows:-From these replies we have learned that the suggestions made in the first teport of the Committee are unacceptable to most of those interested, on one or all, of the following grounds;-(a) number of categories,(b) definition of categories;(c) nomenclature.

Jan 1, 1955

By L. R. Burdick

The Smokescope is an instrument recently developed for determining the density of smoke by shade comparison. The instrument is designed so that the smoke is seen adjacent to two shades of gray corresponding to Nos. 2 and 3 on the Ringelmann chart. Data on smoke density are important in the smoke-abatement field. The method that is specified and accepted as standard for smoke-density determination by the majority of city smoke regulations involves comparing the smoke shade with the four shades on the Ringelmann chart as published by the Bureau of Mines.2/ This investigation was made to determine the accuracy and convenience of the Smokescope. It was conducted as a part of the Bureau I s air-pollution work, which includes the study of techniques that will promote smoke abatement. The accuracy of the Smokescope was arbitrarily defined as the difference between the Smokescope determinations and the determinations by the accepted, standard method and was expressed as Smokescope correction. Although the corrections obtained were strictly correct only for the two observers and the Smokescope of the investigation, they indicate what might be expected from any observer who uses a Smokescope with reference shades that duplicate those of the test instrument. The report is devoted largely to the data on Smokescope correction, which were taken from a single stack under controlled smoke conditions. Field work, which was done at various locations with different stacks, is mentioned briefly in connection with the comparison of the convenience of the two methods. The data for estimating Smokescope correction were taken for the three variables that were expected to affect the results, namely, the density of the smoke, the amount of light, and the color of the sky behind the smoke.

Jan 1, 1955

By Frank Doxey

AT Dominion Steel & Coal Corp. it has long been recognized that continued mechanization of mine operations is necessary in the Pictou, Cumberland, and Sidney coal fields of Nova Scotia. The varied physical conditions in these fields call for special consideration of individual cases before planning is finalized. Because standard equipment cannot be procured which would operate successfully, many experiments have been necessary over the years to keep pace with the progress made in other countries. There are two mines, producing 2000 tpd, located in the Pictou coal field. The field is badly distorted and crossed by many faults. Seams are highly inclined and irregular and vary in thickness from 5 to 40 ft. Entries are difficult to maintain because of squeezing of the coal. ribs and movement of the roof and pavement. Output from the three operating mines in the Cumberland field is 3000 tpd. The field is highly inclined, inclination varying from 12° to 32°. Overlying beds consist of shales and massive sandstone lenses of extreme toughness and are responsible for bumps when the stresses are relieved by extraction. At greatest depth these are among the deepest coal workings in the world. Depth of cover ranges from 2300 to 4000 ft. This prohibits room-and-pillar working and necessitates longwall operation. Working of contiguous seams concurrently to maintain output increases the already difficult conditions. The Sydney field, with a frontage of about 30 miles, is the most important of the Nova Scotia coal fields. With the exception of one small area it is now wholly submarine. Output is approximately 21,000 tpd. Seams are 21/2 to 8 ft thick, and cover in the areas varies from 600 to 2300 ft, with an average of 1500 ft from sea bottom to the top of the seam. The seams dip in a seaward direction, pitches ranging from 6" to 4.0". The shoreline is the last place of entry to the seams and distance from the bank to the working faces is generally over 3½ miles, in some cases as much as 6½ miles. Ventilation is a problem and requires the construction of large permanent airways. Getting and Loading Coal: In 1925, in view of heavy pressures exerted by thickness of cover overlying the seams, roadways and pillars of the room-and-pillar system being worked began to break up and coal was lost. It was decided that a change in the method of extraction in areas with heavy cover was necessary, and experiments were made with many short walls and longwalls varying between 90 and 250 ft. Trial and error proved that the best operating length was between 400 and 500 ft, delivering all coal to the dip, with roadways to the face following a level course. The change-over was gradual, and the technique of roof control developed with the system, so that falls to the face are now very infrequent. An advantage of longwall mining is that it yields 95 pct extraction, especially important in coal seams of high quality or in seams where faults or disturbances restrict the workable areas. This percentage of extraction is based on the fact that the longwall advancing system takes development faces where pitch permits instead of driving headings and leaving roadway pillars. This system yields high tonnage during development and limits loss in extraction to duff left during operations. Accompanying disadvantages, on the other hand, are the heavy construction cost of main roadways and the necessity of driving all new flank face roadways through the gob. If the main roadways are driven through the solid, and large enough pillars are left on each side for protection against flank face weights, then the width of solid coal is approximately 1700 ft. This represents 10.6 pct of the coal available, or 89.4 pct extraction of the whole. These pillars, however, are of such size that they provide a useful pillar drawing area as a final operation of the mine. It may be that although the seam cannot be generally mined by the room-and-pillar method, it can be adapted to

Jan 1, 1955

By C. S. Chang

Replacement of active groups in corn starch, as shown by results of the starch derivatives tested, impairs rather than improves the value of corn starch as a selective iron oxide depressant. Increased ability to depress iron oxides is generally accompanied by a parallel ability to depress quartz. PEARL starch, a corn starch prepared with a minimum of alteration, is a good selective depressant for iron oxide minerals.' From what is known of the complex chemistry of corn starch, there is evidence that it consists of a mixture of saturated giant polymeric molecules, both straight and branch-chained, the constituents consisting of glucose units with hydroxyl radicals as active or polar groups. To add to the existing knowledge of the chemistry of the flotation process, it is desirable to ascertain the effects on the corn starch as an iron oxide depres-

Jan 1, 1955

By J. G. A. Stevenson

"IntroductionDURING the past quarter of a century diamond drilling, in all its phases, has increased in Canada to a very impressive total of more than 10,000,000 feet annually. Since the art of diamond drilling became recognized, some seventy-five years ago, there has been considerable improvement in both equipment and technique. The steam-powered drill rig and the hand-set diamond bit are things of the past.The purpose of this paper is to review some drilling trends •and practices over the past few years. In the preparation of the paper, the author wishes to acknowledge kind assistance of Mr. J. D. Cumming, Dr. C. H. Hitchcock, Mr. Robert H. Quintal, and many others, including staff members of the Longyear organization.Figures provided by the Dominion Bureau of Statistics for the year 1954 show that Canadian production of metallic and non-metallic minerals and structural materials had a value of $1,454.2 million, excluding radioactive products for which figures are not available. Approximately 61 per cent of this valuation comprised production of nickel, copper, gold, coal, asbestos, zinc, lead, and iron. It is certain that diamond drilling played a major role in the discovery and development of the orebodies from which these minerals were obtained.After the surface examination of an ore deposit, diamond drilling will automatically follow, in order to determine structure, grade, and tonnage.Footage drilled by mining companies and contractors on mineral exploration and blast-hole work since 1945, as reported by the Do-minion Bureau of Statistics, is shown in Figure 1."

Jan 1, 1955

By F. A. Forward, J. Halpern

A new process for extracting uranium from ores with carbonate solutions is described. Leaching is carried out under oxygen pressure to ensure that all the uranium is converted to the soluble hexavalent state. By this method), alkaline leaching can be used successfully to treat a greater variety of ores, including pitchblende ores, than has been possible in the past. The advantages of carbonate leaching over conventional acid leaching processes are enhanced further by a new method which has been developed for recovering uranium from basic leach solutions. This is achieved by reducing the uranium to the tetravalent state with hydrogen in the presence of a suitable catalyst. A high grade uranium oxide product is precipitated directly from the leach solutions. Vanadium oxide also can be precipitated by this method. The chemistry of the leaching and precipitation reactions are discussed, and laboratory results are presented which illustrate the applicability of the process and describe the variables affecting leaching and precipitation rates, recoveries, and reagent consumption. THE extractive metallurgy of uranium is influenced by a number of special considerations which generally do not arise in connection with the treatment of the more common base metal ores. Perhaps foremost among these is the very low uranium content of most of the ores which are encountered today, usually only a few tenths of one percent. A further difficulty is presented by the fact that the uranium often occurs in such a form that it cannot be concentrated efficiently by gravity or flotation methods. In these and other important respects, there is evident some degree of parallelism between the extractive metallurgy of uranium and that of gold and, as in the latter case, it has generally been found that uranium ores can best be treated directly by selective leaching methods. It is readily evident that this parallel does not extend to the chemical properties of the two metals. Unlike gold, which is easily reduced to metallic form, uranium is highly reactive. It tends to occur as oxides, silicates, or salts. Two ores are of predominant importance as commercial sources of this metal: pitchblende which contains uranium as the oxide, U3O51 and carnotite in which the uranium is present as a complex salt with vanadium, K2O-2UCV3V2O5-3H2O. These ores may vary widely in respect to the nature of their gangue constituents. Some are largely siliceous in composition, while others consist mainly of calcite. Sometimes substantial amounts of pyrite or of organic materials are present and these may lead to specific problems in treating the ore. Further complications may be introduced by the presence of other metal values such as gold, copper, cobalt, or vanadium whose re- covery has to be considered along with that of the uranium, or whose separation from uranium presents particular difficulty. In general, there are two main processes for recovering uranium in common use today.'.2 One of these employs an acid solution such as dilute sulphuric acid to extract the uranium from the ore. A suitable oxidizing agent such as MnO, or NaNO, is sometimes added if the uranium in the ore is in a partially reduced state. The uranium dissolves as a uranyl sulphate salt and can be precipitated subsequently by neutralization or other suitable treatment of the solution. The second process employs an alkaline leaching solution, usually containing sodium carbonate. The uranium, which must be in the hexavalent state, is dissolved as a complex uranyl tricarbonate salt, and then is precipitated either by neutralizing the solution with acid or by adding an excess of sodium hydroxide. The latter method has the advantage of permitting the solutions to be recycled, since the carbonate is not destroyed. This is essential if the process is to be economical, particularly with low grade ores. With each of these processes, there are associated a number of advantages and disadvantages and the choice between using acid or carbonate leaching is generally determined by the nature of the ore to be treated. In the past, more ores appear to have been amenable to acid leaching than to carbonate leaching and the former process correspondingly has found wider application. With most ores, acid leaching has been found to operate fairly efficiently and to yield high recoveries. One of the main disadvantages has been that large amounts of impurities, such as iron and aluminum, sometimes are taken into solution along with the uranium. This may give rise to a high reagent consumption and to difficulties in separating a pure uranium product. Excessive reagent consumption in the acid leach process also may result

Jan 1, 1955

By C. H. North, L. E. Lynd, W. W. Anderson, H. Sicurdson

Since the composition and structure of the beach sand concentrates correspond so closely to what would be expected of ilmenites that have been altered by oxidation and leaching, there is no reason to postulate the existence of the hypothetical compound, arizonite, to account for the composition of titaniferous beach sand concentrates. The four concentrates studied are examples of the different products that can result from various degrees of alteration of primary ilmenite. CONSIDERABLE uncertainty is revealed in the literature regarding the nature of the titanium minerals which make up the bulk of the heavy, opaque fractions of numerous beach sand deposits of the world. An investigation was made, therefore, of beach sand concentrates of North Carolina, Florida, Brazil, and India. Magnetic concentration, X-ray, and microscope data were obtained which show that these concentrates consist essentially of ilmenite and its alteration products. The alteration, brought about by oxidation and leaching of iron values, has resulted in upgrading the ores to a range of 56 to 64 pct TiO², as compared with 52.7 pct in ilmenite of theoretical composition. Conclusions drawn regarding the nature of the dominant titanium-bearing mineral in beach sand deposits have been based mainly on chemical composition, specific gravity, and petrography. This material has usually been referred to as ilmenite or weathered ilrnenite.: It has also been referred to as arizonite because in chemical composition it resembles an Occurrence in in which was described by Palmer' in 1909. The chemical composition of Palmer's arizonite corresponded closely to the formula Fe²O³ . 3TiOs. From approximate measurements of crystal angles on a large imperfect crystal with rounded faces, the

Jan 1, 1955

By P. E. Busby, C. Wells

FURTHER study of data used in determinations of 1—rates of diffusion of boron in austenite and 2—solubilities of boron in the a and phases of iron and steel' has provided an equation for the diffusion of boron in a iron. In brief, the previously published data were accumulated from the results of deboron-izing (and decarburizing) experiments carried out in the range of 700° to 1300°C. Diffusion coefficients (D?) for boron in austenite were calculated using the Grube solution of Fick's law. However, only solubility values were estimated from the discontinuous concentration-penetration curves, Fig. 1, which are characteristic of diffusion in two phases. Dr. Carl Wagner' has recently provided a solution for calculating D values from penetration curves of this type as follows: Cl1.1 —C8/C8- C11.1 = vp ? e ? erf (?) and D = ?/4?2 t where C11,12, C8, C11, and E have the values shown in Fig. 1. D is the diffusion coefficient, sq cm per sec; t is time of deboronizing anneal, see; and ? is a di-mensionless parameter. For a given diffusion experiment, the value of ? can be readily obtained by graphical solution from a plot of y vs the right-hand part of Eq. 1. D may then be evaluated from Eq. 2. The avplication of this solution to previously re-ported results, of which excerpts are given in Table I, permits the calculation of diffusion coefficients for boron in a iron. On the basis of these meager data, it is tentatively concluded that the diffusion of boron in a may be represented by the equation Da = 1011 e-92,900/RT where R is the gas constant, cal X 0C-1 X mol-1; and T is the absolute temperature, OK. Although the frequency factor, 106 sq cm per sec, is admittedly several orders of magnitude higher than expected, the value of Q, 62,000 cal per mol, appears reasonable and is, in fact, very similar to that for the self-diffusion of iron. It is pertinent to mention at this point that the value of Q obtained for the diffusion of boron in austenite by means of the Wagner solution is 19,000 cal per mol and is in excellent agreement with the value previously reported1 in the equation DT = 2xl0-3 e-21,000/RT [4] which was determined by the application of the Grube solution to other data. The fact that determined constants A and Q in the equation D? = A e-Q/RT were practically the same, independent of whether the Wagner or Grube solutions were used in determinations of D values, strengthened the authors' belief that the computed values of D (Table I) using the Wagner solution are reliable. The relative values in Eqs. 3 and 4 for the diffusion of boron in the a and ? phases, respectively, suggest that boron forms a substitutional solid solution in a iron and an interstitial solid solution in ? iron. The same tentative conclusion has been reached by McBride et al.3 on the basis of relative solubilities, atom diameter, and the size of the interstitial hole in a and ? iron. In connection with the data for test 14 listed in Table I, it is of interest to calculate the solubility of boron in a iron using the D value given by Eq. 3. As might be anticipated from the small movement of the interface in test 14, proper substitutions in Eqs. 2 and 1 give a low value, approximately 0.0004 pct B, at 850°C. Apparently at 835°C (test 13) it is possible to obtain 0.0018 pct B, and at 850°C only 0.0004 pct B into solution in the a phase before a second phase appears. These observations are consistent with the Fe-B constitution diagram proposed by McBride, Spretnak, and Speiser.3 References P. E. Busby, M. E. Warga, and C. Wells: Diffusion and Solubility of Boron in Iron and Steel. Trans. AIME (1953) 197, p. 1463; Journal of Metals (November 1953). 'W. Jost: Diffusion in Solids, Liquids, Gases. (1952) pp. 69-71. New York. Academic Press Inc. "C. C. McBride, J. W. Spretnak, and R. Speiser: A Study of the Fe-Fe2B System. Trans. ASM (1954) 46, p. 499.

Jan 1, 1955

The Black Hills Mineral Atlas briefly summarizes all important data available on the mines and mineral deposits in the Black Hills that have been explored, developed, mined, or located. The purpose of the atlas is threefold; First, from available data the general potentialities of the Black Hills region can be determined, although it is not possible to calculate actual ore reserves; second, it will provide the necessary basic information regarding a given property or commodity for further detailed study; and third, the compilation is a comprehensive directory of Black Hills deposits.

Jan 1, 1955

By H. Wilton Clark

VARYING in thickness and in number from place to place, coal seams in the Canadian Rockies also range in pitch from nearly horizontal to vertical, sometimes with overturns. Over the entire coal-bearing area there are considerable differences of rank in coals of the same geological age, and there are marked differences in ash content and wash-ability characteristics. Correlation of seams at mining operations within a few miles of each other has often proved impossible. These factors influence mining methods, and, of course, production results. The oldest coal formations of western Canada are of Lower Cretaceous age, as the carboniferous sediments are marine and contain no coal. Coal is also present in formations of Upper Cretaceous and Tertiary ages. The rank of coal varies from semi-anthracite in some operations in the Kootenay and Luscar formations of the Lower Cretaceous in the Rockies to lignite in the Tertiary fields of the Saskatchewan prairies. Fig. 1 shows the general extent of the formations. The pitching seams, chiefly Lower Cretaceous, occur in the western belt of the Rocky Mountain foothills and the eastern slopes of the Rockies themselves. (The road to Tent Mt. strip pit, elevation 7000 ft, is shown on p. 832.) Formations extend from the U. S.-Canadian boundary for several bundred miles in Alberta and continue for a similar distance in British Columbia. Present geological estimates show a probable reserve of the order of 25,000 million tons of coal ranging from high volatile bituminous to semi-anthracite, with a large percentage of coking coal, constituting one of the major world reserves of that type. It should be noted that although the quoted estimate probably errs on the conservative side, the question of access to the seams in a mountainous terrain will always be a problem; a wide divergence may exist between actual reserves and the quantities of coal economically recoverable. An excerpt from the Canadian government Report of the Royal Commission on Coal 1946 states that conditions favorable to coal formation were intermittent and these intervals relatively brief in comparison with periods in which no coal was formed. Conditions were favorable to the growth or accumulation of vegetation in one area, while fresh water sediments and marine shales were being deposited in other areas. During periods of emergence the coal deposits were subjected to erosion or were covered by coarse sands and gravels from the mountains, whereas during submergence they were covered by fine clays deposited in embayments of the sea. During some of the periods of coal formation, volcanic activity deposited beds of fine volcanic ash and dust with the coal-forming vegetation. Coal deposits reach their greatest development in the mountains and thin rapidly to the east into the plains area, where they are deeply buried beneath younger sediments. For example, in the Fernie area of southeastern British Columbia there are in places 22 seams having an aggregate thickness of 150 ft in a stratigraphic interval of 3500 ft, whereas at Cole-man in the Alberta Crowsnest area the measures are only 800 ft in thickness and contain a maximum of five seams aggregating about 47 ft of coal. At Belle-vue, 10 miles further east, the measures are reduced to 430 ft with only three seams aggregating about 37 ft of coal. Subsequently the tremendous forces involved in the upthrust of the Rocky Mountains produced great displacement of the coal-bearing formations and at the same time a change in geologically young coals from low to high rank. The floor or footwall of most seams consists of carbonaceous shales, which are almost as adaptable to bending as the coal seams themselves. The seams show very few cleats or cleavage planes and have been so weakened structurally that as mined 50 pct or more will pass through a ¼-in. screen, seldom

Jan 1, 1955

By L. E. Wilsey, W. G. Bearden

This paper presents results of analysis of the effect of fracturing on initial flow rates and on ultimate recoveries from low capacity oil formations. This analysis shows that even in formations of permeability as low as 0.1 md, large fracture treatments can yield oil recoveries and production rates approaching those of high permeability formations. Field production information is shown which supports the analytical work. INTRODUCTION Often hydrocarbon bearing formations are discovered which, while they are known to contain large quantities of oil, will not produce at commercially attractive rates without special well stimulation. Attempts to solve this problem led to the development of such techniques as underreaming, shooting, acidizing, and recently hydraulic fracturing. These methods of stimulation have been highly successful in many fields. All of these treatments, however, affect only the pay section near the well bore and therefore owe their success to circumventing and overcoming local permeability reduction about the well bore. It has been the belief that in treating wells to stimulate production in which there is no permeability reduction near the well, the maximum possible production rate increase would be of the order of two or fourfold. Hence, it has been concluded that fracture treatment of uniformly low capacity (permeability times thickness) formations could meet with but limited success. It is the purpose of this paper to show that the use of fracture treatments much larger than usually used can yield commercially attractive producing rates and high recoveries even in formations of permeability less than 0.1 of a md. PROCEDURE In order to illustrate the effects of fracturing, an analytical study of some hypothetical systems was made in which one factor at a time was varied to show what is important in recovering oil from fractured wells. It was assumed that a horizontal fracture of relatively high fluid-carrying capacity extended from a well bore. The presence of such a fracture will cause a marked influence on the flow pattern and pressure distribution in the formations, with the net effect being to reduce tremendously the resistance to flow into the well bore. A diagram of the resulting flow pattern and pressure distribution is illustrated in Fig. 1. Immediately after production commences, the principal flow of fluid is vertically from the formation flanking the fracture, into the fracture, and then into the well. After sufficient oil and gas have been produced to lower the pressure in the formation adjacent the fracture, oil and gas will begin to flow in a radial manner into the fracture from the formations beyond the end of the fracture. In calculating the performance under such conditions. the material balance or conservation of matter equation and equations of flow were solved simultaneously by a stepwise method of calculation. Flow rates were found by determining the pressure distribution, as illustrated

Jan 1, 1955

By W. F. Kieschnick, and W. J. McGuire&apos, Eugene Harrison

This paper concerns the induction and extension of fractures into rock formations as involved in drilling, completing, and production stimulating operations on wells. Conclusions concerning formation breakdown are derived from (I) a review and extension of published analyses relating to mechanical theories of rock stress and the state of stress in the earth's crust and (2) a correlation of field data from fracturing operations. Conclusions concerning the mechanics of fracture extension, which indicate the relationship between fracture dimensions and rock properties, depth, and volume of injected fluid, are tentative and largely establish limits of relationships. These conclusions are derived from stress calculations, limited field data, and laboratory experimental studies. The experimental work involves the study of the stresses at the fracture boundaries and the geometry of pressurized fractures by means of photo-elastic modeling methods. Results of this investigation indicate that a large majority of pressure induced wellbore fractures are vertical, particularly in deeper wells; and variations in the pressures necessary to create and extend fractures can be explained largely on a basis of established rock properties. It is also shown that variations due to tectonic forces should usually be expected to be slight. Other results indicate that during that extension of fractures rather large fracture volumes are temporarily created by the parting of the formation. The purpose of this paper is to present the results of calculations and laboratory experiments concerning the mechanics of fracture induction and extension with a view to broadening existing knowledge relating to these phenomena. It is believed that continued progress in developing knowledge of this type is important to the further development of techniques for drilling and completing wells. When a wellbore is subjected to sufficiently high pressure, fracturing of the formation surrounding the well occurs. This phenomenon is a common cause of lost circulation during drilling operations, is a deliberately planned factor in most squeeze cementing operations, and is the controlling factor in many productivity stimulation operations. The exploitation of formation fracturing in recent years has been particularly impressive in sand-viscous fluid well stimulation treatments which were first introduced to the industry by the Stanolind research group1,2,3 several years ago. The borehole fracturing phenomenon has been analyzed mathematically by application of the principles defining the elastic and inelastic behavior of thick-walled cylinders of homogeneous, isotropic, and impermeable material.1,5,6 This basic argument is re-presented in this paper along with new considerations which strengthen it. In addition to these arguments relating to fracture induction some calculations and experimental results relating to the mechanics of fracture extension are presented. Since the nature of the pressure induced fracture at distances from the well is of great importance in considerations of well stimulation procedures there appears to be a need for an integrated approach which deals with the mechanics of fracture extension as well as with wellbore rupture.

Jan 1, 1955