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By J. F. Shea, O. F. Tangel

Battelle Memorial Institute participated in a program for the General Services Administration aimed at developing a nickel-cobalt separation process that could be integrated in the Nicaro nickel plant. At the time the programwas being carried out, the Nicaro process was a straight-through operation, in which the ore was reduced and leached, after which the pregnant solution was boiled to produce a so-called "bulk precipitate" which contained virtually all of the nickel and cobalt which had been dissolved in the leaching step. The weight ratio of nickel to cobalt in Nicaro ore is approximately 15 to 20:l. The weight ratio of nickel to cobalt in the finished product had to be 100:l or higher to meet specifications. Because the Nicaro process embodied no nickel-cobalt separation step, the only way that a bulk precipitate of the specified nicke1:cobalt ratio could be produced was to so adjust roasting and leaching conditions that nickel would be selectively leached and most of the cobalt would be rejected with the tailings. The required selectivity, however, was achieved at the expense of nickel recovery, which was 5 or more per cent less than might have been obtained with the existing equipment, utilities, man power, etc., had selectivity been no object. The over-all purpose of the program was to develop a separation step that could be fitted into or onto the Nicaro facilities and which would permit the manufacture of a product that would meet the desired specifications and still permit the recovery of a maximum amount of nickel. Battelle suggested that this might be accomplished by reprocessing off-specification bulk precipitate and specifically suggested the process based on ammonium sulphate leaching followed by hydrogen reduction of the leach solution according to techniques developed commercially by Sherritt Gordon Mines Limited. Such a process would not only satisfy the objectives of the research but would present two additional advantages. (1) It would produce a separate cobalt product which could be further processed into metal, alloys, oxides, or salts. (2) It would yield nickel in metallic form which might be more generally marketable and command a slightly higher price per unit of nickel than the Nicaro oxide product. DESCRIPTION OF THE PROCESS Figure 1 is a flowsheet of the process. The essential features are: (1) Extraction of about 97 per cent of the nickel and about 85 per cent of the cobalt from bulk precipitate by a principal leach with ainmonium sulphate solution (Step A). Extraction of virtually all of

Jan 1, 1961

By R. F. Shurtz

The problem of estimating the precision of systematic samples from a mineral deposit is attacked by interpolating the quality, or other attribute measured, by using Fourier approximation. Such approximation using trigonometric functions yields a particularly simple expression for the variance of the mean value of the attribute sampled. The increasing volume of publication in which the science of statistics has been applied to the problem of predicting the quality of an ore deposit from sets of samples taken from it might lead one to believe that engineering judgment can be replaced by statistics. There is, in fact, an implicit application of the principle of indifference or of "no advance knowledge" which has been discredited in modern statistical theory and practice. These pages will show that it is not always advantageous, efficient, or safe to apply this principle. This problem will be dealt with by using series of orthonormal functions to describe the distribution of the quality of ore in space as contrasted with the more commonly used distribution of quality as a frequency function. Mining engineers are rarely well acquainted with the use of such series or of the functions comprising them. These uses are commonplace in the fields of communication and information theory and it is not surprising that applications taken from these fields should be found appropriate for the analysis of the information contained in a set of samples from an ore deposit. It is hoped that presentation of the following basic, but incomplete, results will generate wider interest in this method and a fuller development of it as well as of the necessary computational techniques. FUNDAMENTAL PREMISES Random variables in the strictest sense are not very common in mine sampling. The sets of samples are almost always taken systematically and are, hence, not subject to all the laws governing random events. Therefore, unless there is indeed random experimental error in the determinations of quality, the treatment of systematic samples of n members as though they were random samples of n members often leads to calculation of confidence limits for the mean quality which are larger than they should be with the result that unnecessary additional sampling is done. The reason for this will emerge in the following discussion leading to Eq. 24 and its generalization. In order to inquire into such questions on a rigorous basis and at the same time avoid arithmetic complications that would obscure the concepts involved, a one dimensional distribution of quality will be assumed. The quality, Q, in suitable units is expressed as a function of the distance, x, along some straight traverse of the deposit. Such a function

Jan 1, 1967

By L. Moyd, P. Moyd

The first commercially available portable gamma ray-neutron beryllium detector, the Rerylometer, was developed by the same group that developed the first practical portable scintillation counter, the Scintillo-meter. This group includes Professor George Brownell, of the Geology Department of the University of Manitoba in winnipeg, and his associates, K. I. Roulston, R. w. Pringle, and R. L. Funt, of the Physics and Engineering Departments of the University of Manitoba. A prototype model was tested in the field by Dr. Brownell during the summer of 1958. Commercial production was undertaken shortly thereafter by Nuclear Enterprises Ltd., of Winnipeg, and a license for manufacture and distribution in the U.S. was granted to Isotopes Specialties Co., of Burbank, California, a division of Nuclear Corporation of America. Early in 1959, we were retained by the 'Mining Division of Minerva Oil Co. to Legin a search throughout North America for minable deposits of beryllium, and to train members of their permanent staff to continue the program. The project included literature sur-veys, interviews with members of various federal, state, and provincial agencies, scanning of our own collection of suites of specimens from various mineral occurrences, and the examination of deposits in the field. The value of a beryllium detector to this program was obvious and arrangements were made to procure one as soon as possible, which resulted in our obtaining and using the first instrument that was produced commercially in the U. S. In addition to the commercially available Berylometer, Mr. William Vaughan and his associates, of the U. S. Geological Survey Geophysics Division, in Denver, have developed and tested several experimental instruments based on the same principles. DETECTOR Principles The detection of beryllium is based on the fact that "hard" gamma rays (1.6 MEV and geater), such as those produced by Antimony convert ordinary beryllium (Be9) to Be8 , with the release of a neutron. The neutrons are counted by a scintillator designed to favor neutron responses while suppressing those of gamma rays. 'The instrument is completely selective for beryllium. No other element can interfere. Instrunlentation The Rerylometer itself, which is cylindrical, is about 8 inches in diameter, 13 inches high, and weighs about 11 pounds. (Figs. 1, 2). The principal components include: 1. A disc of wax to moderate (or "thermalize") neutrons. 2. A boron-enriched polyester-zinc-sulphide fluorescent screen. This material produces strong flashes when struck by thermalized neutrons but only weak flashes from gamma rays. 3. A photomultiplier tube. 4. An electronic circuit, complete with one srnall 71/2-volt dry battery. The photomultiplier tube and electronic circuit convert neutron flashes to electrical impulses, but gamma ray effects are almost

Jan 1, 1961

By L. W. Pommier, F. B. Brien, A. K. Bhasin

In the field of mineral processing, although many operations are applied to suspensions of ore particles in fluids, there is a lack of fundamental knowledge relative to the flow resistance encountered by immersed bodies moving through solid-liquid suspensions. Previously proposed equations, based on the Ostwald-de Waele (power-law) model for non-Newtonian fluids, are exam ined in the turbulent flow region relative to a number of pertinent variables and their effects on the movement of immersed bodies. As more knowledge is acquired in regard to the effects of suspension variables on the rheological properties, useful relationships may be proposed to allow predictions of conditions to achieve optimum results for engineering purposes. In the field of minerals processing, many operations are applied to suspensions of ore particles in fluids. The differential movement of solids of various sizes and densities in suspensions is of utmost importance to gravity concentration, wet classification, flotation, hydrometallurgy, and pipeline transport of solids. The subject is also of importance to other branches of engineering; for example, those involved with soil mechanics, ceramic slips, and oil-well drilling fluids. There is a lack of fundamental knowledge relative to the flow resistance encountered by immersed bodies moving through solid-liquid suspensions. The problems encountered in the direct application of the well-known Stokes and Newton's Laws to non-Newtonian systems have been examined in a previous paper.' Equations were proposed based on the Ostwald-de Waele (power-law) model for non-Newtonian fluids. This present paper examines these equations in the turbulent flow region relative to a number of pertinent variables and their effects on the movement of immersed bodies. It is thought that, as more knowledge is acquired as to the effects of suspension variables on the rheological properties, useful relationships may be proposed to allow prediction of conditions to achieve optimum results for engineering purposes. The purpose of this paper is to make an initial assessment of the nature and magnitude of pertinent suspension variables. In order to avoid too voluminous a document, the examination of kinetics and mechanisms will be omitted at this time. THEORY A Newtonian fluid is defined as a fluid in which the stress is proportional to the rate of strain, 2 i.e.: H = viscosity; see Table I. for list of symbols The following equations are conventionally used to assess the motion of spherical particles moving under laminar and turbulent flow conditions through Newtonian fluids: When these relationships are applied in practice to suspensions, the liquid density is substituted by a composite suspension density, and viscosity is usually taken as that of the suspending liquid or an approximated "apparent viscosity." However, suspensions are non-Newtonian in character3 and thus, more than one viscosity parameter is required to describe their behavior. A number of models have been proposed for non-Newtonian fluids;2,4 among these the simplest is the Ostwaldde Waele or power-law model for incompressible fluids which for one dimensional flow may be reduced to:

Jan 1, 1970

Organization Place Date 1919 American Society of Civil Engineers..: Twin Cities, Minn. June 17-20 American Society of Mechanical Engineers Detroit, Mich. June 17-20 American Institute of Chemical Engineers Boston, Mass. June 18-21 American Drop. Forge Association Pittsburgh, Pa June 19-21 American Institute of Electrical Engineers Lake Placid, N. Y. June 24-27 American Society for Testing Materials Atlantic City, N. J. June 24-27 Society for Prom. of Engng. Education Baltimore, Md. June 25-28 American Chemical Society Philadelpia, Pa. Sept. 2-6 National Assn. of Stationary Engineers Huntington, W. Va. Sept. 8 American Peat Society.. Minneapolis, Minn. Sept. 22-24 American Iron; Steel Electrical Engineers St. Louis, Mo. Sept. 22-26 American Institute of Min. and Met. Engineers, Chicago, Ill. Sept. 22-27

Jan 6, 1919

Jan 1, 1965

By C. J. Beevers

Tlze influence of zirconium hydride precipitate mprphology on the fructure of Zr-H alloys tested at strain rates of 10- sec at 20° and - 196°C and at strain rates of -500 sec.-1 at 20°C has been inves-tigated. The critical stage in the embrittlement of these alloys was the fracture of the zirconium hyhide precipitates to form large interval cracks at a stress of 25,000 10 137,000 psi. In specimens con-temping up to 100 ppm H the preciptates existed as isolafed platelets in the zirconium matrix and their fracture as enhanced by low temperature (—196°C) and high strain rate (-500 set-f) loading. These resl~lts lead to the conclusion that the rate of strain hardening of the zirconium metal controls the frac-tzrm of the hydride platelets. Increased hydrogen contents of 500 to 2000 ppm resulted in an increase in the 1)volume fraction and size of precipitates and crlso led to crack propogation in the hydride at both 20 and —196C at the low strain rates (10'* sec-'). Quenching led to refinerment of hydride precipitate size and reduced the degree of embrittlement at — 196°C; this effect is attributed to the absence of fracture of the fine precipitates. The formation of zirconium hydride precipitates has been shown to be the cause of hydrogen embrittlement of zirconium.' Several investigators'-" have studied the problem in broad outline, demonstrating that impact-loading conditions, testing temperatures below room temperature, and increasing hydrogen content produce increased brittleness. For example, Muehlenkamp and schwope2 showed that the transition temperature for notched impact tests was raised from 150" to 350°C on increasing the hydrogen content from 45 to 490 ppm. The degree of embrittlement is also controlled by the morphology of the zirconium hydride precipitates. The solubility of hydrogen in zirconium decreases from 600 ppm at 550°C to 10 ppm at 20"C,~ so that the form of the zirconium hydride precipitates (ZrH2) can be modified by varying the cooling rate through the Zr-aZr + ZrH2 phase boundary.= Forscher showed that quenching a specimen containing 35 ppm H from above 315°C resulted in a reduction in area of 70 pct at -196"C, whereas slowly cooling from above 315°C resulted in a ductility of half this value. The role of the hydride precipitate in the fracture process has been examined by Young and schwartz6 and more recently by westlake.' From metallo-graphic observations on slowly cooled Zr-H alloys they have suggested that cracks are nucleated in the hydride precipitates by the interactions of twins in the zirconium metal with the hydride. The experiments reported in this paper show that crack propagation in the zirconium hydride precipitates is the critical stage in the embrittlement of Zr-H alloys. The factors influencing fracture of the hydride precipitates and crack propagation in the zirconium metal will be related to the problem of embrittlement. EXPERIMENTAL TECHNIQUES The zirconium used in these experiments was produced from an ingot of vacuum arc-melted iodide zirconium forged down to 1 in. diameter at 800' to 850°C. The 1-in.-diameter bar was surface-machined and cold-swaged to 0.375 in. diameter. After a vacuum anneal at 800°C for 1 hr the hardness was 60 to 70 Vdh. The total impurity content was approxi-

Jan 1, 1965

By S. R. B. Cooke, H. S. Choi, I. Iwasaki

In a previous article1 the function of various fatty acids as collectors for iron ores was reported for the two alternate processes; (a) the flotation of iron-oxide minerals, and (b) the flotation of calcium-activated siliceous gangue. The selectivity of separation was shown to be markedly dependent not only on such common parameters as pH and the levels of collector and activator addition, but also on the structure and the degree of unsaturation of the acids used. The iron ores employed consisted primarily of hematite, goethite, and quartz and as the effectiveness of any one acid on the separation depends on the individual response of each constituent mineral toward the given collector, a comprehensive knowledge of the floatability of the individual minerals is desirable for the interpretation of the results obtained. The mechanism by which a collector ion becomes attached to a mineral-solution interface has been a subject of much investigation. From quantitative studies of the properties of the electrical double layer on mercury2 and on several solid surfaces3,4,5,6 , the adsorption of some flotation reagents at the mineral-solution interface is beginning to be understood. For example, it has been demonstrated from streaming potential measurements made on quartz5 and corundum6 that the interfacial electrical condition is strongly dependent on the pH. Thisoccurs presumably through the following electrolytic reaction at the interface, and in the presence of a flotation collector, controls the floatability of the solids. A concurrent investigation of the flotation behavior of goethite and of quartz carried out at the School of Mines and Metallurgy7 has shown a positive correlation with the electrokinetic behavior of these minerals. The purpose of the present investigation was to collect general information on the floatability of hematite, and to investigate the function of various 18-carbon aliphatic acids on the floatability of hematite, goethite, and of activated quartz. Electrophoretic mobility measurements, simplified flotation tests using a modified Hallimond tube, and contact angle and frothability measurements were employed. The results are of direct application in the interpretation of the batch flotation results on natural ores as

Jan 1, 1961

By C. G. Cheriton

The Bathurst mining district is located near the town of Bathurst on the north shore of the province of New Brunswick in eastern Canada. This region is the northeasterly extension of the Appalachian mountain system. The area is heavily forested and covered with a fairly uniform layer of glacial gravels and boulder clay. The relief is low, increasing to a few hundred feet in the north west and several hundred feet in the extreme southwest. Thus, rock outcrops are scarce and occur mostly along streams and ridges. These factors made conventional prospecting difficult and resulted in the district becoming an excellent place for the application of regional geological studies, air photo techniques, airborne and gound geophysical methods and soil sampling. Late in 1952, The Brunswick Mining and Smelting Company discovered a very large base metal sulphide body presently known as their No. 6 orebody. Early in 1953, another and even larger sulphide body was discovered and is known as the No. 12 ore body. Mining exploration was very active thoughout 1953 and in 1954, The American Metal Company discovered the orebodies which have been developed into The Heath Steele 'Mines. The location of these deposits is shown on figure one. In the latter part of 1954, The Anaconda Company became interested in the district and decided to make a geological study of this new and promising base rrietal area. The following paper presents the story of the application of modern geological and geophysical techniques, leading to the discovery of a large sul-nhidp liodv. The Bathurst district is generally underlain by the Tetagouche group of Middle Ordovician rocks.

Jan 1, 1961

By J. W. Givens, P. B. Crawford

A potentiometric model study has been made of the effect of vertical fractures existing in the matrix of the reservoir on the flooding or cycling performance. Fractures can have unusual flow characteristics. Fluid entering one side of a fracture can emerge on either the same or opposite side of the fracture, depending on the particular streamline. Fracture orientation has a great influence on the sweep efficiency. However, sustained fluid injection may still permit large areas to be swept. INTRODUCTION One can find considerable information available in the literature on the effect of fractures originating at the wellbore on sweep efficiencies of water-flooding or gas cycling programs.1-5 However, there arc few, if any, quantitative data reported in the literature on the effect of vertical or horizontal fractures existing out in the reservoir matrix on secondary recovery performance. Several papers have been presented on the effect of vertical and horizontal fractures on the productivity or conductivity of waterflood and gas injection patterns, but in all cases the fractures initiated at the well and simulated commercial fractures.6,7 It is believed that natural fractures may exist out in the reservoir matrix and would effect the displacement performance. The purpose of this report was to study the effect of a few isolated vertical fractures existing out in the reservoir matrix on the performance of waterflood or gas injection patterns. DESCRIPTION AND EQUIPMENT Since the potentiometric model was described by Lee8 it has been widely used to study numerous types of fluid displacement problems. The potentio- metric model can be used for fluid displacement studies when the following assumptions are valid: (a) steady-state conditions exist; (b) the mobilicy ratio is one; and (c) the capillary and gravitational effects can be neglected. Five-spot and direct line drive square patterns were studied using a copper strip of the desired length and orientation to simulate a vertical fracture in the reservoir matrix. The 20 x 20-in. model was considered to represent only one element of an infinite array of similar patterns. DISCUSSION AND RESULTS FIVE-SPOT PATTERN — ONE FRACTURE BETWEEN INJECTION AND PRODUCING WELLS Fig. 1 shows a quadrant of a five-spot pattem with the vertical fracture existing out in the matrix along a line connecting the injection and producing wells. Length of the fracture was equal to 35.4 per cent of the distance between injection and producing wells. In this particular pattern it is noted that fluid breaks through from the injection well to the producing well when the dimensionless time is equivalent to 26.9. Dimensionless time is defined as volume of fluid injected divided by the volume of displaceable fluid in the pattem expressed as a per cent. The cross-hatched areas of this

Jan 1, 1967

By K. Takahashi, I. Iwasaki

it is well known1 that racemic mixtures of optical isomers can be separated by passing their solutions through a column packed with r- or 1-quartz powder so that one of the isomers becomes adsorbed selectively on the asymmetric quartz surfaces. Although the natural occurrence of r- and 1-quartz is more or less equally distributed, some localities show enough deviations toward a higher proportion of l-quartz2 to suggest that optical isomerism might influence quartz flotation. Beta-amines have an asymmetric carbon atom, and therefore optical activity may be expected. Beta-amines are reported to behave quite differently from alpha-amines in the flotation upgrading of certain oxidized iron ores.3 It is of interest, for both practical and theoretical reasons, to determine whether or not optical isomerism plays a role in the amine flotation of quartz. In this article the results of Hallimond tube flotation tests and of adsorption measurements using d-beta-phenylisopropylamine on both r- and 1-quartz are compared. D-beta-phenylisopropylamine was chosen for the tests because it is commercially available in optical isomers. MATERIALS AND METHODS Brazilian quartz crystals were hand-sorted according to the difference in trigonal trapezohedral faces, and each crystal was further checked by the Airy's spiral.4 The respective crystals were then crushed, and the -150 + 200-mesh fractions were screened out for the Hallimond tube tests. The samples were cleaned by brief leaching with warm, dilute hydrochloric acid, and then by repeated rinsing with distilled water. In preparation for the adsorption measurements, they were then dry-ground in a pebble mill for several hours, washed a few times with distilled water, and finally dried in a vacuum desiccator. By means of the Krypton gas adsorption method, the specific surfaces of r- and 1-quartz samples were determined to be 27,700 and 19,800 sq cm per gm respectively, the difference being due mainly to the decantation procedure rather than to the inherent difference in their grindability. D-beta-phenylisopropylamine was the only collector used in the study. It was solubilized by neutralizing with 110% of the stoichiometric requirement of 0.1 N hydrochloric acid. The specific rotation of the d-beta-phenylisopropylamine was determined with a polari-meter using sodium D line to be, Although the d-beta-phenylis~prop~lamine showed absorption maxima in the wave length region of 250 to 270 millimicrons, due presumably to the phenyl group, these peaks were too sensitive to be used for colorimetric determination of the residual concentration in the adsorption measurements. The amine-picrate method, used in the colorimetric analysis of dodecylammonium chloride,' was found to work satisfactorily for the d-beta-phenylisopropylamine. The adsorption densities were thus determined after equilibrating 40 gm of the ground quartz sample with 300 ml of solution by tumbling in separate glass-stoppered Erlenmeyer flasks for one hour. EXPERIMENTAL RESULTS Fig. 1 presents the adsorption densities of d-beta-phenylisopropylamine on the r- and 1-quarts in the pH range of 6 to 7.5. In agreement with data reported in the literature, the adsorption density of d-beta-phenylisopropylamine was slightly higher on the r-quartz than on the 1-quartz, although the difference was not as pronounced as one might expect from the capacity of r-quartz and 1-quartz to separate racemic

Jan 1, 1969

By L. A. Roe

Magnetic separation of iron ores is one of the fastest-growing segments of the minerals beneficiation industry. The tonnage of taconite ores processed annually by magnetic separation will, in a few years, reach 100 million. Magnetic separation occupies an attractive position in the field of ore beneficiation. It is a simple yet effective method, used for some 150 years and steadily growing more important. This type of beneficiation orginated in 1792, when William Ful-larton was issued a British patent covering the separation of iron ore by magnetic attraction. What is magnetism, and why are some materials capable of being magnetized and others not The study involves many unknowns, and even a partial answer to these questions would be a dissertation in solid state physics and perhaps other fields of science. But the last two decades have revealed basic facts as to why certain materials are magnetic and what happens to them when they are magnetized. Some of the newer studies in solid state physics have developed a theory that can be applied to studies of magnetism. It is claimed that magnetism stems fundamentally from the spin of electrons in atoms that tend to go in pairs, spinning in opposite directions. The atom as a whole can act as a magnet only when there is an imbalance of electronic spin. Whenever an atom has an odd number of electrons, therefore, this imbalance exists. This neutralizing effect explains why a piece of material that contains atomic magnets is not necessarily magnetic. The physicists tell us that iron is composed of many small magnetized regions called domains, which consist individually of millions of atoms. The piece of iron becomes magnetized when an external force lines up these domains in the same direction. Fundamental data developed by physicists working in fields far removed from minerals beneficiation are now available for developing better magnetic separators for ore processing. More Data Needed on Magnetic Properties of Minerals: There is less information on magnetic properties of minerals than there is for certain aspects of magnetic separator design. When the data on magnetic properties is available, it is often directed toward the study of powders for tape recorders and other highly scientific endeavors that are of little use to the beneficiation engineer. W. R. Crane's table of tractive forces, published in 1902, is still a guide in the study of magnetic minerals. Bits of other information regarding electrostatic conductivity, dielectric constant values, and permeability of various minerals have also appeared but are of small practical value in magnetic separation of ore. It is extremely important to obtain pure mineral specimens for making investigations and to record results that may be of use in studies of magnetic processes. Reference to the large volume of data developed by those concerned with analysis and design of permanent magnets soon reveals that these people have extensively evaluated the effect of various impurities on magnetic properties. Much of the science of the ferrite industry is based upon spinel-type structures which are varied by substitution of selected elements or even subtraction of elements, leaving vacant sites in the space lattice. Magnetic separators are used to beneficiate a wide variety of industrial minerals. In this application the relatively large volumes of nonmagnetics are usually the commercial products. The amount of mag-

Jan 1, 1959

By C. Y. Wen, H. O. HOPMAN

l. INTRODUCTION. IN casting a thermal balance of the heat generated and absorbed in a blast-furnace treating lead-, copper- and similar non-ferrous ores, assumptions have always to be made for the values of the heat of formation of slag. ? Considering that the larger part of the charge introduced into the furnace comes out in the form of slag, the significance becomes apparent of a lack of heat-values for the singulo-silicate, which is the type of slags commonly made. The aim of the present investigation is to supply these heat-values as far as possible with the apparatus and the time available. The heats of formation of the ferrous and manganous bi-silicates have been determined by Le Chatelier; 1 those of some silicates other than iron and manganese by Tschernobaeff:2 finally Richards 3 gives a figure for a copper blast-furnace slag of known composition. The existing data and those resulting from the present investigation are assembled in Table VI. II. MATERIALS USED. The materials used in the experiments were silica, ferrous oxide, and calcium carbonate. Silica.-The silica sold in the market as chemically pure usually contains small amounts of magnesia, lime, and alumina, and is therefore not suited for the work. The pure material was obtained from clear quartz crystals from Arkansas, broken in a diamond mortar and ground in an agate mortar to pass 1 Comptes rendus, vol. cxx., p. 623 (1895); vol. cxxii., p. SO (1896). 2 Revue de Métallurgie, vol. ii., p. 729 (1905); Electrochemical and Metallurgical Industry, vol. iv., No. 2, p. 72 (Feb., 1906). 3 Electrochemical and Metallurgical Industry, vol. v., No. 7, p. 266 furls?, 1907;) ; Metallurgical Calculations, vol. iii.,.pp. 474, 475 (1908).

Jul 1, 1910

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

The Grand Isle sulfur mine is located in the Gulf of Mexico, approximately seven miles off the coast of Grand Isle, Jefferson Parish, La. The deposit is on acreage covered by oil, gas, and mineral leases originally issued in favor of Humble Oil & Refining Co. by the State of Louisiana which were continued, maintained, and redesignated by the U.S. Department of the Interior after passage of the Outer Continental Shelf Lands Act. The sulfur deposit was discovered in 1949 when Humble Oil & Refining Co. penetrated more than 200 ft of sulfur-bearing limestone in a zone between 1813 and 2075 ft below sea level. In 1954, Humble drilled ten more sulfur prospect holes, eight of which encountered sulfur ore. On September 19, 1956, Freeport Sulphur Co. acquired from Humble Oil & Refining Co, the sulfur rights underlying the tracts, and the actual design of the installation began the same month. The first structural contract was awarded in December 1957 and offshore erection began in June 1958. The initial phase of construction has been completed and production by the Frasch process commenced in April 1960. The estimated total cost of the project is $30 million, of which $8 million is the extra cost incurred by the necessity of offshore operations. More than $22 million was expended before production was started. GEOLOGY OF DEPOSIT Grand Isle is the third largest sulfur deposit in the U.S. The orebody embraces several hundred acres, but its outer limits are yet to be defined to the northeast, east, and south. Most Gulf Coast sulfur deposits occur in a caprock mantle of calcite (referred to as limestone), anhydrite, and occasionally gypsum, which covers the apex of an intrusive mass of salt. Commercial quantities of sulfur are usually confined to the calcite or limestone member. Most often such limestone is completely enclosed by dense anhydrite below and impervious sediments above, which effectively form a closed reservoir. The depth of the Grand Isle orebody ranges from 1800 ft to 2500 ft below sea level. Within the present boundary, the sulfur-bearing limestone varies in thickness from 220 ft to 425 ft, while the sulfur content varies an average of about 15 pct in the leanest hole to an average of about 30 pct in the richest. Rock containing less than 5 pct sulfur is not classed as ore, and holes assaying less than 20,-000 long tons per acre of sulfur in place are not considered commercial offshore. The sulfur enrich-

Jan 1, 1961

By F. W. Jessen, C. C. Patton

Adsorbed films were formed on polished stainless steel specimens from dilute benzene solutions of two crude oil distillation residua. Although the two residua were extremely dissimilar in composition, contact angle measurements showed that the two films increased the wettability of the steel specimens to oil by equal amounts. Furthermore, the wettability of the films was essentially unaffected by the desorption techniques used. Paraffin deposits were formed from heptane-wax solutions on the same stainless steel specimens. These deposits definitely adhered to the surface. Presence of an adsorbed crude oil film on the metal surface increased its free surface energy and resulted in increased deposition of paraffin. The addition to the heptane - wax solution of small amounts of the same distillation residua that were used to form the adsorbed films resulted in decreased cohesive strength in the deposits formed, which resulted in decreased deposition. The presence of a crude oil fraction both in the solution and as a preadsorbed film eliminated the adherence of a deposit of any kind. A mechanism of deposition is proposed which explains the results obtained. INTRODUCTION The natural formation of any predominantly organic accumulation in oilwell tubing, surface flow lines or other production and storage facilities is called a paraffin deposit. These deposits restrict the production of crude oil, causing a substantial increase in production costs because of decreased flow capacity, expense for periodic deposit removal and unproductive downtime. The conditions under which such deposits form, their physical characteristics and the nature and severity of the problem created are extremely varied. Over the past several years, much progress has been made in developing and utilizing methods to remove accumulated paraffin deposition. However, like so many other problems, the basic stumbling block appears to be a lack of understanding of the fundamental mechanism involved in the formation of such deposits. Crude petroleum is known to contain considerable quantities of polar, surface active substances which Doddl has shown to be present at the oil-water interface. Denekas, Mattax and Davis2 observed that the wettability of reservoir rocks was drastically altered by exposure to crude oil fractions; and Zisman, et a1.3 showed that the nature of the compounds adsorbed on a surface would determine its wettability characteristics. Cole and Jessen4 and Ehrig5showed that surface wettability can have a profound effect on the magnitude of paraffin deposition, and Parks6 demonstrated chat the presence of certain adsorbed films on a metal surface would reduce the adherence of paraffin to that surface. Zisman7 has since advanced the theory that the conditions for adhesion are the same as for wetting. Therefore, it was felt that there was adequate evidence to support the supposition that adsorption of compounds from a crude oil might play an important part in paraffin deposition. ADSORPTION-WETTABILITY EXPERIMENTS Initial experiments were conducted to determine the effects of adsorption from solution of crude oil residua on the wettability of a polished stainless steel surface. Distillation residua with initial atmospheric boiling points of 700F were used in preference to the whole crudes in order to concentrate on the molecular weight range of interest, and to eliminate the possibility of composition change due to evaporation of the light ends. Also, these high boiling materials would be expected to be adsorbed from the whole oil in preference to similar compounds of lower molecular weight.

Jan 1, 1966

By R. R. Joseph, K. A. Gschneidner

The solid solubility of magnesium in the close-packed modifications of lanthanum, cerium, praseodymium, neodymium, gadolinium, dysprosium, and lutetium was determined from approximately 250°C to the eutectoid temperature by the X-ray parametric technique. The maximum solubility at the eutectoid temperature was found to be 9.4 at. pet in La, 8.2 in Ce, 9.2 in Pr, 8.2 in Nd, 14.1 in Gd, 13.5 in Dy, and 11.5 in Lu. The solubility when compared at a homologous temperature was found to increase in a smooth manner with decreasing size factor from lanthanum to lutetium. It was found that the apparent atomic radius of magnesium when dissolved in the lanthanide solvent was constant and could be accounted for by consideration of several models dealing with departures from Vegard's law. The eutectoid temperatures for the lanthanide-rich La-Mg, Ce-Mg, and Nd-Mg systems were found to be 544", 505°, and 551°c, respectively. A study of the solid solubility of magnesium in the lanthanide metals was initiated because the valency and electron egativity difference are essentially constant and favorable for solid-solution formation, and thus one could examine the effect of size on terminal solid solutions. The size factors based on metal radii range from 14.6 pet for lanthanum to 7.5 pet for lutetium. Since the electronegativity difference is small, 0.06 unit or less, application of the Hume-~othery' and Darken and Gurry2 criteria for solid-solution formation indicates that the solubility of magnesium would be expected to be small for lanthanum (between 5 and 10 at. pet) and to increase as we proceed along the lanthanide series. A search of the literature revealed no data on the solubility of magnesium in the lanthanide metals except for the solubility of magnesium in cerium at 450oCA typical phase diagram for the lanthanide-rich end of the lanthanide-magnesium phase diagram is shown in Fig. 1. EXPERIMENTAL PROCEDURES Preparation of Alloys. The lanthanide metals used in the preparation of alloys for this investigation were prepared from the corresponding fluoride by metallothermic reduction techniques previously described by Daane.4 The chemical analyses of the metals used are listed in Table I.

Jan 1, 1965

Born, March 28, 1853 Died July 23, 1916 On July 25, 1916, the Board of Directors adopted the following minute and directed that it be entered upon the records of the Board & published in the Bulletin of the Institute, and thereof be sent to the family of Mr. Kirchhoff: Charles Kirchhoff was one of the oldest, most widely known and most highly esteerned members of the American Institute of Mining Engineers. On his return in 1875 from a European course of study, to begin a highly successful professional career, he joined the Institute, then just commencing to acquire both national and international recognition. He became at once, and-for more than 40 years continued to be, its earnest , and active supporter, serving it as Manager, Councilor or Director for terms aggregating 9 years,-as Vice-President for 2 years, and twice as President for a year. During the critical period of the erection of the United Engineering Society's building, and the transfer of the Institute to permanent head-quarters therein, Mr. Kirchhoff was its efficient representative in the United Engineering Society, and on the Building Committee. In 1910, amid the congratulations of colleagues, employees, and innumerable friends, Mr. Kirchhoff retired from active business as Vice- President and General Manager of a great technical publishing company. Yet he sacrificed of his well-earned leisure yet one more year, to serve the Institute as President through 1911.

Jan 9, 1916

By Olav Mellgren

Part I. The interaction between potassium ethyl xanthate and lead salts has been studied thermo-chemically. It is shown that ethyl xanthate reacts with lead carbonate, basic carbonate, thiosulfate and sulfate according to principles of simple chemistry, whereas reactions with lead sulfite, metasulfite, basic thiosulfate and hydroxide at high pH are associated with secondary reactions. A new compound "xanthogen thiosulfate" is postulated. Part 11. Adsorption of ethyl xanthate on galena has been studied quantitatively and thennochemi-cally. It is shown that an ion-exchange mechanism governs the adsorption process and that the heat of adsorption of xanthate on galena is equivalent to the heat of reaction of ethyl xanthate with bulk lead salts. It is concluded that the entropy content of the surface "compound" on galena is different from that of a corresponding bulk lead salt. Alkali depression is in part shown to be due to the instability of the xanthate-galena system at high pH and to the formation of basic lead salts. Sulfate and carbonate ions are shown to have a stabilizing effect on the xanthate-galena system. PARTI. THERMOCHEMISTRY OF ETHYL XANTHATE AND OF ITS REACTION WITH LEAD SALTS In the past little attention has been paid to the chemistry of lead xanthate. It is known that xan-thates form slightly soluble compounds with lead and that suspensions of lead xanthates in alkaline solution decompose rather readily.' The solubility of lead ethyl xanthate is of the order of 2.6 x 10-6 moles per 1. At increasing pH the xanthate concentration of a saturated solution contains more xanthate. Thus at pH 11 this xanthate content is about 100-fold larger than at pH 7.1 Xanthates are known to be consumed when added to a suspension of slightly soluble lead salts such as lead sulfate and lead carbonate. It is unknown to what extent this xanthate consumption is due to a simple chemical reaction because, frequently, observations are made which reveal secondary reaction products in such reactions. Thermochemical study of the reaction between xanthate and lead salts offers a means to clarify the significance of these reactions as the enthalpy changes can be accurately predicted from heat of formation of lead salts in pure solution reactions. In the present work the heats of formation of lead ethyl xanthate from potassium ethyl xanthate and lead salts are determined and some thermochemical aspects of xanthate in solution are studied. The results of these investigations are presented in Part I. In Part II the heat of adsorption of ethyl xanthate on galena surfaces is presented. All enthalpy changes were measured directly in a microcalorimeter. Calorimeter: The calorimeter used for measuring enthalpy changes was similar to that used by Redinha and Kitchener2 which was based on a description by Derbyshire and Marshall.3 Other useful references4,5 are listed. A sketch of the calorimeter

Jan 1, 1967

By H. E. Hawkes, D. A. Barr

Time variations in the copper content of the sediments of streams draining mineralized areas were studied in two areas of contrasting climatic environment, one in northern and one in southern British Columbia. In each area, samples were collected and observations made of rainfall, stream discharge and air and water temperature at intervals throughout the summer season. Samples were analyzed for total and cold-extractable copper. Results showed a weak inverse relation between cold-extractable copper and discharge in two out of the three test sites in the southern area, and a decrease in ratio of COld-extractable to total copper over the duration of the test period at a highly anomalous site in the northern area. In suspended rock flour resulting from glacial erosion of mineralized rock in the northern area, virtually all the copper was found to be soluble in cold, dilute hydrochloric acid. None of the variations observed is sufficient to cause serious problems in geochemical sediment surveys. Systematic collection and trace analysis of stream sediments has seen wide application in recent years as a method of primary prospecting in primitive areas. Common practice is to collect fine-grained samples of sediment either from the active channel or from the flood plain near the channel. Samples are dried, sieved and the -80-mesh fraction analyzed after breakdown of the sample by a relatively strong attack, such as by fusion or by treatment with hot perchloric acid. Drying, sieving and rigorous chemical attack requires established facilities, either in a well equipped central laboratory or in base camp. Thus analysis for total metal involves a substantial delay from the time the samples are collected until the analytical data can be reported. An alternative system uses a cold aqueous extrac-tant in place of the hot acid or flux.4 Advantages of the cold-extraction techniques are that kits can be prepared for use directly at the sample site and that, in some problems, the patterns in cold-extractable metal, usually abbreviated cxMe, are more useful as ore guides than the patterns in total metal.' In the course of operational geochemical sediment surveys, a problem that has come up repeatedly is failure to reproduce anomalous values or patterns by resampling the same areas. The mystery of the vanishing anomaly has led to speculation as to whether there is a significant variation in the metal content of sediment samples with the weather or with the time of year. Review of the published literature shows that a number of experiments have been carried out on time variations in the metal content of stream water.1,2,5,7-9 The only published report on time variations in stream sediments that has come to the authors' attention, however, is by Govett,3 working in Northern Rhodesia.

Jan 1, 1963

By K. W. John, L. Mueller

The rock mechanics approach to stability problems of steep rock slopes dealt with in this article has particular reference to the concept and methods of analysis developed by the Salzburg, Austria, school of rock mechanics. These theories are based on the principal postulate of the anistropy of the technological properties of in-situ rock masses. The present approach, which is more in line with geological engineering concepts, differs distinctively from the soil mechanics and engineering geological concepts commonly practiced in the United States. PRINCIPAL ENGINEERING APPROACH TO GEOTECHNICAL PROBLEMS AVAILABLE ENGINEERING CONCEPTS At the present time two different concepts are available for engineering analysis of underground structures and foundations in different earth material: soil mechanics and rock mechanics. Of these two branches, soil mechanics is, after 40 years of initially revolutionary and more recently evolutionary development, well established. Its principal concept of replacing in-situ soils or rock masses by perfectly homogeneous substitues has resulted in many practicable methods of analysis which, if applied with judgement, have resulted in successful applications throughout the world. Conversely, rock mechanics is still in the early stages of revolutionary development. Few, if any, standard concepts or methods of analysis have been established. Opinions vary widely. At present the professional background of an investigator very often determines the engineering concept to be applied to a particular problem, rather than its actual requirements if considered objectively. This paper stresses the rock mechanics or geological engineering point of view advocated by the Salzburg group. A review of the soil mechanics concepts is considered beyond the scope of this paper. THE "SALZBURG APPROACH" TO ROCK MECHANICS The rock mechanics concept as outlined here was initiated by Stini, based upon work by sander.1 Since

Jan 1, 1963