Search Documents

By Waldemar Lindgren

The following pages present data accepted by many geochemists and geologists regarding the succession of minerals and the temperatures of formation in ore deposits affiliated with igneous rocks. They also present the individual views of the author on the composition of the solutions that were active and on the mode of deposition. He does not regard these views as speculations or hypotheses but as forming a well motivated and consistent theory. It is not certain, however, that all investigators will subscribe to them. Introduction The mining engineer may not always be interested in the field of stability and temperature of origin in the mineralogy of ore deposits, but he certainly is interested in the succession of minerals because this has a definite bearing on the understanding of the ores and on the best processes of extraction. It is proposed, therefore, to summarize in plain language the principal features of succession as shown in metallic ores. Chemical analyses of ores are always important, but the real knowledge of succession—sometimes called paragenesis-—of ores has been gained only in the last 20 years, by the study of polished sections. The study of hand specimens threw much light on the subject—as shown, for instance, by Breithaupt, whose "Paragenesis," written a hundred years ago, is still useful—but the results have been modified by our slowly gained understanding of the processes of replacement. Indications of Temperature Melting Points.—In the first place, a distinction must be made as to whether the ore is a product of magmatic consolidation, of pegmatitiza-tion or of hydrothermal activity. Most of the ores fall in the latter class. In any case, the melting points, although of importance, are not definite indications. In a magma the oxides and sulfides are likely to be among the earliest crystalline products (magnetite, ilmenite, zircon, corundum,

Jan 1, 1937

By E. T. Turkdogan

The activities of SiO2, FeO, and Fe2O3 are calculated from previous experimental data on the activity of oxygen in Fe-Si-O melts at 1550°C. Using the oxide-activity data, the free energy of formation of fayalite from its oxides is evaluated for 1550°C. A number of investigators1-4 contributed to the study of the state of oxidation of iron in SiO,-FeO-Fe,O3 melts and the phase equilibria in the system Fe-Si-O. In a more detailed study, Schuhmann and Ensio5 and Michal and Schuhmann% easured the state of equilibrium in the SiO,-FeO-Fe,O3 melts saturated with y-iron or silica or both under low-oxygen potentials and within the temperature range 1250" to 1350°C. Similar measurements were also made by Turkdogan and Bills7,' over wide ranges of composition and oxygen potentials at 1550"C. Using the experimental data on the oxygen activities in the ternary system, Schuhmann' calculated the activities of silica and ferrous oxide in Si0,-FeO-Fe2O3 melts for 1350°C. Adequate knowledge on the activities of the constituent oxides of melts is essential in the study of reaction-equilibria and reaction-kinetics in oxide-melts. With this in view, the activities of oxides in SiO2-FeO-Fe2O3 melts at 1550°C are computed using the experimental data of Turkdogan and Bills7'8 on the oxygen activities in these melts.

Jan 1, 1962

By Joseph A. Sutton, John D. Corrick

The continuing depletion of high-grade ore de- posits in this country has created a need to develop more effective methods for recovering valuable metals from low-grade ores. The use of microorganisms for their biochemical reactions is one possible way to solve certain phases of this problem. Bacteria have been used successfully by many diversified industries. Until recently, however, little attention has been focused on the use of bacteria in mining and metallurgical processes. This report summarizes one phase of the microbial studies being conducted at the U.S. Bureau of Mines, College Park Metallurgy Research Center. The two-fold objective of this study was, first, to determine if pure strains of the bacteria Ferrobacillus ferrooxidans, Thiobacillus concretivorus and Thiobacillus ferrooxidans could utilize the iron and sulfur occurring in sulfide minerals to produce appreciable quantities of ferric sulfate and sulfuric acid for dissolving copper and, second, to develop the chemistry involved in the microbial oxidation of sulfide minerals. These are of particular interest as they relate directly to the feasibility of employing microorganisms in leaching operations.

Jan 6, 1963

By J. E. Powell, F. H. Spedding

WHILE rare earths are reported to be widely distributed in nature and are not really rare," in practice, there are only a few minerals which are sufficiently rich in rare earths to serve as practical sources. Perhaps the best known of these is monazite which is a phosphate mineral containing rare earths and thorium. This mineral occurs as a dense brown sand in gravel beds and is particularly rich in the light rare earths of the cerium subgroup. This mineral is processed commercially for its thorium, cerium, and lanthanum content, and, consequently, furnishes rich concentrates from which neodymium, praseodymium, samarium, europium, and gadolinium may be obtained. Unfortunately, monazite is rather lean in rare earths heavier than gadolinium. A second mineral which is rich in the light rare earths is bastnasite, a fluoro-carbonate. Extensive deposits of this ore have been discovered in the western United States and have received considerable newspaper publicity in recent years. While bastnasite is very rich with respect to cerium, lanthanum, and neodymium, it contains even less heavy rare earths than does monazite. One of the better sources of heavy rare earths of the yttrium subgroup is gadolinite, a black silicate rock from which the rare-earth content can be extracted readily by acid leaching. It is obtained chiefly from Norway at the present time, although there are known deposits in the United States. Other sources of heavy rare earths include fergu-sonite, euxenite, and samarskite which are refractory tantalo-columbate ores. These minerals require caustic fusion or reduction to carbides with carbon before the rare-earth content can be extracted. All of the minerals which are rich in the heavy rare earths contain yttrium as a major constituent. After the rare earths have been extracted as a group from an ore by chemical means, it is generally convenient to precipitate them from acid media with oxalic acid in order to eliminate certain non-rare-earth impurities such as iron, beryllium, etc., which are usually present. The oxalate can then be readily ignited to R2O3. The oxide can be dissolved in acid and is the starting point for subsequent separation into the pure components. Perhaps the principal reason why the rare earths have not been studied as extensively as other elements of the periodic table, whose natural abundances are comparable, is that they are extremely difficult to separate from each other by the usual chemical means. Prior to 1945, the separation of one trivalent rare earth from another was a laborious process. All separations were based on repeated fractionation processes, i.e., fractional precipitation, fractional decomposition, fractional crystallization, etc. These processes were repeated from a few hundred to many thousands of times in order to obtain individual rare-earth salts of reasonable purity. Of course, mention should be made that, in the few cases where a rare earth could be oxidized or reduced to a valence state other than three, more conventional chemical means could be utilized to separate the oxidized or reduced ion from the other normally trivalent rare earths. The ionic states which deserve special mention are CeIV, SmII, Eu11, and Yb11. When it is possible to remove an element of the series efficiently, due to an optional valence state, its immediate neighbors also become easier to isolate. For example, binary mixtures of lanthanum and cerium, and praseodymium and cerium can be obtained by a relatively small number of fractional operations. The tetravalent state of cerium then allows the complete resolution of the binary mixtures by ordinary chemical means. Although the tetravalent state of cerium has been known for a long time, the divalent states of samarium, europium, and ytterbium were not used extensively in separations prior to 1930 because they are relatively unstable in aqueous media.'-" No attempt will be made to give a comprehensive review of the extensive literature dealing with the separation of rare earths. Rather, this paper will be confined to a review of those methods which have been developed at Iowa State College during recent years, and which have proved extraordinarily successful for the isolation of highly pure rare earths in quantity. It was obvious that, if pure rare earths were to become generally available, methods would have to be developed wherein the thousands of fractional operations made necessary by the similarity of rare-earth properties could be performed automatically. The development of chromatographic techniques and ion-exchange resins appeared to offer a mechanism by which this objective could be accomplished. A number of early attempts were made to separate rare earths by these means; for example, Russell and Pearce12 passed a mixture of rare earths through a cation-exchange column and reported

Jan 1, 1955

By J. E. Burke, C. S. Barrett

THE fine lines shown in Fig 1 are typical of markings that may be detected after polishing and etching deformed specimens of alpha brass and other alloys. Although they have long been the subject of discussion by metallurgists their nature is still uncertain and the names that have been applied to them, such as deformation lines or strain markings, indicate this uncertainty. In this paper which reports the results of a further investigation of their nature, they will be called strain markings. INTRODUCTION Matthewson and Phillips1 in 1916 concluded that strain markings appeared only after deformations that exceeded 20 pct. They objected to the markings being called slip lines believing this term should be reserved for surface markings produced by plastic deformation. In 1921, Vogel2 described similar striations which appeared after polishing and etching the roughly ground surface of numerous alloys. He reported that the markings were crystallographic in nature, and since they resemble Neumann bands in iron, at least superficially, he assumed them to be mechanical twins. In 1928, Matthewson3 reported work by Phillips which indicated that the lines were more readily produced by impact than by slow deformation and that in many cases the twins inside recrystallized grains were parallel to strain markings in the original deformed grains. This was taken as evidence that the markings coalesce into annealing twins, and hence that they themselves are mechanical twins. Many attempts have been made to [ ] demonstrate directly that the markings are mechanical twins. In 1934, Samans4 described the results of X ray studies of two deformed crystals of alpha brass. Evidence was obtained which could be interpreted to indicate that the strain markings are mechanical twins, and this remains the only direct evidence to this effect. Several other attempts to obtain similar evidence by X ray diffraction have failed5,6,7 although in no case was the original method of Samans employed. An

Jan 1, 1948

By Carle Hayward

AT THE February, 1916, meeting of the Institute, a paper presented by Hayward and Raymond gave the results of a study on the effect of time in tempering medium-carbon steel, when the following conclusions were reached: It is not fair to consider the question settled when only three specimens were used for each treatment, but the results obtained indicate that for reheating quenched medium-carbon steel to temperatures below 500° it is only necessary to heat it through. Longer heating has little or no effect on the tensile strength, ductility, or hardness. At temperatures above 500°, increasing the time of treatment causes a slight falling off in hardness and tensile strength with a corresponding increase in ductility. In the discussion of the paper these conclusions were attacked and evidence presented that seemed to throw doubt on their accuracy. The authors, however, showed that this evidence was based on high-carbon or alloy steels and no facts regarding medium-carbon steel were presented. During this study the heat treatment was carried out in a small electric resistance furnace. It held nine specimens, but when these were placed in the furnace the temperature was lowered to such an extent that 30 to 40 min. were required to reach the desired heat. The authors pointed to this as a weak point in the investigation and it seemed wise to supplement the research by work on similar steel but using a different method of heating. This has been done and the results are given in the present paper. The Rhode Island Tool Co. cooperated by furnishing the steel and turning the tensile specimens.

Jan 1, 1922

By C. H. Mathewson

ABOUT fifty pages of Henry M. Howe's profound treatise, "The Metallography of Steel and Cast Iron," are devoted to twinning with special reference to the origin, nature and general significance of the Neu-mann bands in ferrite. Howe believed with Osmond and Cartaud1 that the Neumanns are mechanical twins and his careful observations leave no doubt that these straight-sided narrow bands habitually occur parallel to trapezohedral planes of form {211}. Attempts to develop the structure of the bands by various methods so that their identity could be established beyond question have not been conspicuously successful. Howe thought that they deflected slip bands. Some of the etching figures which have been developed within and adjacent to Neumann bands support the contention that they are twins. A good example of this effect in ferrite containing 0.6 per cent. of nickel and 1.3 per cent. of phosphorus, originally due to Harnecker and Rassow,2. was reproduced in the 1928 lecture before the Institute of Metals Division on twinning in metals.3 In this case, the sides of the figures might represent the traces of cubic planes laid bare by etching a properly oriented grain of ferrite, twinned along a plane of form 12111. Our own observations in this direction may be represented by Fig. 1 which shows in a deeply etched cavity in the boundary region between a Neumann band and the original crystal two small crystal surfaces which resemble the faces meeting at a reentrant angle in the simple cube twinned along a bisecting plane of form {211} as sketched in Fig. 2. Rosenhain and McMinn4 in 1925, after a careful study of slip bands in ferrite containing Neumanns previously produced by shock, concluded

Jan 1, 1928

By T. B. Counselman

PROBABLY the earliest concentration of iron ore in this country was carried on in the northeastern magnetite areas. Magnetic concentration was relatively simple and gave a concentrate that, after agglomeration, and in spite of being high in phosphorus because of the dry concentrating methods then in use, was satisfactory blast-furnace feed. Production from the northeastern magnetite area languished after the discovery and development of the Lake Superior ores, where there was seemingly an unlimited tonnage of high-grade ore, first the Michigan ores, and subsequently the still larger deposits of Minnesota. For years only the higher grade, direct shipping ores of the Lake Superior district were mined. Those of Michigan, and of the Vermilion Range in Minnesota, were hard ores and came principally from underground mines. The softer ores of the Mesabi came partly from underground mines, but mostly from the enormous deposits that could be worked by open-pit methods. The costs of ore from these open-pit deposits, even with the high initial cost of stripping, were so low that the underground mines of the Mesabi could hardly compete. The so-called Old Range ores, of Michigan and of the Vermilion Range of Minnesota, were hard and lumpy, and opened up the burden in the blast furnace, therefore making possible harder driving with greater output. Also, some of these ores were of such grade and physical characteristics that they were suitable for charge ore in the open hearth. These ores, therefore, commanded a price premium, and could compete with the softer, finer, but cheaper, Mesabi ores. The big tonnage reserves, however, are on the Mesabi, and it is these big open-pit deposits that constitute our stock pile of iron ore, from which we are drawing so heavily during this war period. On the western end of the Mesabi the ore was found to be high in silica, and not suitable as furnace feed. As early as 1902, attempts were made to concentrate this so-called wash ore and by 1910 the first washing plant was put into operation. The process was very simple, consisting essentially of a sizing and washing operation, with scalping screens, logwashers, and tables, which later were replaced by classifiers. Ore particles finer than 100 mesh were deliberately wasted, because these fines were undesirable in the furnace. Fortunately, these tailings were impounded, and already are being reworked. Before long some of the low-grade ores began to require more elaborate treatment than the simple washing operation and, tables having been discarded because of their low capacity, in favor of classifiers, jigs were next introduced. These were able to discard coarser pieces of tailing than classifiers. Jigs are in active use today, various improvements having been made in their design and application. Various other machines and methods of concentration have been tried from time to time, and have in turn been discarded for more improved processes. The latest and most important process that has been

Jan 1, 1943

By C. E. Dobbin

THE identification of rock formations by a study of certain physical characteristics of burned samples was introduced in Wyoming in 1,926, when W. G. Buckles, superintendent. of the brick department of the Parco Development Co., reported to officials of the Producers & Refiners Corpn. that shales from the Cretaceous and older formations exposed between Parco and Rawlins exhibited distinctive coloration and textural features when burned in a standard brick kiln at temperatures ranging between 1000° and 3000° F. In collaboration with Elfred Beck, chief geologist of the Producers & Refiners Corpn., Buckles later burned cuttings and cores from several Wyoming wildcat wells in a standard kiln and successfully identified certain subsurface formations which had not been satisfactorily identified by other means. The results of their investigations were outlined in papers presented by Beck before the American Association of Petroleum Geologists at San Francisco in March, 1928, and by Buckles at. a joint meeting of the Rocky Mountain Oil and Gas Association and the Production Division of the American Petroleum Institute at Casper in November, 1928. These papers have not been published. The investigations set forth in this paper were carried out for. the purpose of determining the value of certain ceramic tests in assisting the petroleum engineers of the U. S. Geological Survey to identify well cuttings that represent Cretaceous shales penetrated beneath unconformable Tertiary formations in central, and eastern Wyoming, but that yield neither lithologic nor paleontologic criteria for satisfactory correlations with distinctive weathered outcrops. The investigations were made in the chemical laboratories of the Geological Survey at- Midwest, Wyo., and consisted of studying certain physical characteristics of burned bricks from representative outcrop samples of unweathered Cretaceous shales and of similarly burned cuttings of the same shales collected from wells in the Salt Creek oil field.

Jan 1, 1931

By Sheldon P. Wimpfen

RESEARCH is undertaken to find out what must be done when what we are doing now is no longer adequate. To accomplish this end, researchers apply the truths of nature to industrial evolution. A survey conducted with the co-operation of 58 universities and colleges offering degrees in mineral engineering was the basis for the table accompanying this article. This survey was undertaken with the object of presenting to faculties and student bodies, as well as to industry, all available information on what action the educational institutions of the country have taken to provide the properly trained researchers so vitally needed. A hoped for result is that the great variety of opportunities available will encourage some undergraduate students to continue in their field beyond attainment of a B.S. degree.

Jan 1, 1947

By H. Biloni, R. Morando

The surface structure and substructure of Al-Cu alloys solidified as conventional ingots and under particular conditions such as those used by Bower and Flemings are studied. The influence of lampblack coating on the mold walls is especially considered and the results compared with those obtained in copper and graphite molds where no coatings exist. When high heat extraction conditions exist the observations show that mechanism of copious nucleation is responsible for most of the chill zone. When the heat extraction through the mold walls is low, a coarse grain structure with dendritic morphology arises, with a size that depends on the degree of convection present, analogous to that analyzed by Bower and Flemings. In both cases the effect of the convection on the macroscopic and microscopic appearance is discussed. The ingot macrostructure consists of one or more of three zones: "chill zone", "columnar zone", and central "equiaxed zone". The mechanism of the columnar-equiaxed transition has been subject of considerable interest and at present at least three theories exist about the formation of the equiaxed region: 1) the constitutional supercooling theory1 maintains that the equiaxed crystals nucleate after the columnar zone has formed, as a result of the constitutional supercooling of the remaining liquid; 2) chalmers2 pointed out, however, that there were several objections to this proposal, and that consideration should be given to the possibility that all the crystals, equiaxed as well as columnar, originated during the initial chilling of the liquid layer in contact with the mold; 3) Jackson et aL3 and O'Hara and ~iller~ suggested that a remelting mechanism of the dendrite arms is responsible for the formation of the equiaxed region. After the work of Cole and Bolling and other authors6 it became evident that convection (natural, reduced, or forced) plays a very important role in the transition from columnar to equiaxed and on the size of the resultant equiaxed structure. Until recently the accepted explanation of the chill zone was that it occurs as a result of copious nucleation in the liquid layer in contact with the mold walls.798 The columnar region is a subsequent result of the growth of favorably oriented grains and, as a result of a selection mechanism studied by Walton and Chalmers,9 elongated grains with marked texture are formed. Recently, however, Bower and Flemings" using an ingenious laboratory experiment introduced the idea that the "copious nucleation" mechanism is not responsible for the formation of the chill zone and that the presence of convection, introducing some form of "crystal multiplication", plays a decisive role in the formation of the chill zone. Unfortunately, it is important to consider that for their conclusions Bower and Flemings extrapolated the results obtained in their special experiments to the case of conventional ingots, and that these authors only analyzed the macrostructures of the specimens. Let us consider the work by Biloni and chalmers" concerning predendritic solidification. These authors were able to show that a study of the segregation substructure of A1-Cu gives information about the nucleation and growth of crystals formed in contact with a cold surface. A spherical predendritic region characterizes the first part of every grain nucleated in contact with the surface as a result of the chill effect. The aim of this paper is to elucidate through the observation of the segregation substructure the conditions under which (in the Bower and Flemings type of experiments and in conventional ingots) either the nucleation or the multiplication mechanism gives rise to the structure in contact with the mold walls. I) EXPERIMENTAL TECHNIQUES The experiments were performed on two alloys: Al-1 wt pct Cu and A1-5 wt pct Cu. The purity of the aluminum was 99.99 pct and the copper 99.999 pct. The results obtained with both alloys were similar. In the Bower and Flemings type of experiments the apparatus employed to obtain rapid solidification against a surface was similar to that used by those authors. The liquid was drawn by partial vacuum into the thin section mold cavity. Plate casts were 5 cm wide and usually 7.5 cm high. The thicknesses of the cast were 0.1 and 0.3 cm. Two different materials were used for the mold, copper and nuclear-grade graphite. The internal mold surfaces were polished and left uncoated for some experiments. In other experiments, the copper or graphite surface was coated with a thin film of lampblack material. In some of these particular experiments one of the mold walls was left with an uncoated region (usually in the form of a cross). The conventional ingots were cast in graphite or copper molds. In different experiments the mold walls were sometimes uncoated or coated with lampblack material. The results obtained in conventional and Bower and Flemings copper molds were compared with those obtained with copper molds coated with a very thin film of graphite; the results obtained were essentially similar. The size of the conventional ingots was 5 cm diam and 7 cm high in all cases. The cast surfaces produced by the Bower and Flemings type of experiments and conventional methods were observed macroscopically and microscopically without any metallographic preparation. As Biloni and Chalmers showed," the observation of the chill surface can give considerable information about the structure and segregation substructure.

Jan 1, 1969

By T. N. Dixon, J. E. Briggs

A study was made of numerical techniques for solving the large sets of simultaneous equations that arise in the mathematical mode ling of oil reservoir behavior. It was found that noniterative techniques, such as the Alternating Direction Implicit (ADI) method, as well as some other finite difference approximations, produce oscillatory or unsmooth results for large time steps. Estimates of time step sizes sufficient to avoid such behavior are given. A comparison was made of the Point Successive Over-Relaxation (PSOR), Two-Line Cyclic Chebyshev Semi-Iterative SOR (2LCC), and iterative ADI methods, with respect to speed of solution of a test problem. It was found that, when applicable, iterative ADI is fastest for problems involving many points, while 2LCC is preferable for smaller problems. INTRODUCTION With the advent of high speed, large memory, digital computers, there has been an increasing emphasis on the development of improved methods for simulating and predicting reservoir performance. Two-dimensional, three-phase reservoir models with various combinations of PVT effects, as well as gravity and capillary forces, are common throughout the industry. Such models are also available through consulting firms, to anyone desiring to use them. Three-dimensional models will probably be practical in only a few years. We conducted a study of some of the numerical methods used for solving the large sets of simultaneous equations that arise in such models. A typical set of equations for a reservoir model is shown below:

Jan 1, 1969

By R. McNeill, D. E. Weiss, E. A. Swinton

In a continuous countercurrent exchange process, an alteration in any one of the operating conditions has a complex effect on the others, which can only be predicted by employing the transfer unit or the theoretical stage theory on a basis of trial and error. A simple method is described for illustrating diagrammatically the behavior of a counter-current system, the equations being simplified by means of a concept the maximum hypothetical exchange performance. An example based on a typical metallurgical system is given, in which a divalent metal is recovered from a dilute solution, the resin being regenerated continuously by a monovalent ion. Useful conclusions are drawn from a study of the theory. Practical methods for performing continuous ion exchange are discussed, and the development of equipment based on modified ore dressing jigs is described. A swinging sieve jig contactor is evaluated experimentally. DURING the last decade, the new synthetic ion exchange resins have been applied extensively in industries outside the field of water treatment, but there is no record of a continuous counter-current process operating on an industrial scale. Attempts have been made to devise a satisfactory process but many problems remain to be solved. The basic principles of continuous processes will be outlined, as well as the major problems in their operation and the progress made in the CSIRO laboratories toward the development of satisfactory industrial techniques. In the metallurgical field ion exchange resins can be used for various applications such as the recovery and concentration of valuable metals from mine waters,' the regeneration of pickling and plating liquors," the prevention of pollution by waste effluents and the recovery of the constituents from them," and the purification of valuable metals such as the rare earths by chromatographic fractionation on columns of ion exchange resins.7,8 . Turther applications undoubtedly will be found in the field of hydrometallurgy where the use of ion exchange resins would enable direct extraction of the desired metal ion from the filtered leach liquor or the leach pulp. For example, an ion exchange process has been described recently for the extraction of gold from a cyanide leach pulp." A continuous process would have advantages in many applications over the usual process employing a fixed bed and intermittent cycle. In a recovery process, it would yield a product stream of steady purity and concentration, it would waste less water in rinsing, and if the contacting apparatus were efficient less resin would be used, since each portion of the resin would be cycled as soon as it was loaded instead of lying idle until the whole bed was ready for regeneration. A very major advantage is that it would be simpler to control automatically. It is probable that continuous operation will be the key for really large scale applications of ion exchange. The flow sheet of a continuous ion exchange recovery-concentration process is illustrated diagrammatically in Fig. 1. Dilute liquor containing the valuable ion flows through the stripping section countercurrently to a moving bed of resin and leaves after a final contact with freshly regenerated resin. The resin leaves the unit almost in equilibrium with the incoming liquor and then flows to the regenerating unit where it is treated by a slow countercurrent flow of concentrated regenerant solution. The adsorbed ion is displaced from the resin and appears in the concentrated product stream. The resin then must pass through a rinse unit or section where regenerant entrained by the resin is washed back into the regeneration section by water. The regenerated and washed resin is then recycled back to the stripping section. I. Theoretical Operating Behavior of Continuous Ion Exchange Stripping System The simple theory of continuous ion exchange is analogous to that of solvent extraction and other diffusional transfer operations and is governed by the equilibrium relationship, the mass balance, the rates of mass transfer, and the contacting efficiency of the unit. Equilibrium Relationship—The relative affinity of two ions A and B, for a particular resin immersed in their solution, can be expressed by plotting compositions of the solution against compositions which exist in resin in equilibrium with those solutions, i.e. C/Co vs q/a where C, is the total normality of the solution, C is the normality of ion A in the solution, a is the total exchange capacity of the resin in gram equivalents

Jan 1, 1956

By David P. Shoemaker, Clara B. Shoemaker

It has been shown for an important class of complex transition intermetallic compounds (a, P, R, 6, and p phases) characterized by "normal" coordination [CN12 (icosahedral), CN14, CN15, CN16/ that interatomic distances nay be calculated to a good approximation as the sum of characteristic atomic radii. Two radii, one for major ligands and one for minor ligmds, are specified for each atom, except in the case of CN12 where only a miaaor-ligand radius is specified. The same appears to be true of transition-metal phases of simpler struc-ture: Laves phases (CN12, CN16), and p-tungsten phases (CN12, CN14). In the case of known examples of the more complex phases, a simple rule is given which specifies these radii. However, only a fraction of the known examples of the simpler phases obey this rule closely. To include the latter phases the rule may be modified by considering the radii as linear functions of the weighted average of the Pauling CN12 radii of the two kinds of atonzs, with the radii weighted according to the over-all chemical composition of the alloy. With very few exceptions interatomic distances for both tlze complex and the simpler transition phases can b$ predicted with this modified rule to within 0.06A. ManY intermetallic compounds are known of composition A,By, in which A is a transition element to the left of the manganese column in the periodic table and B is a transition element in or to the right of it. Frequently the coordination numbers (CN) found in these compounds are CN12 (icosahedral), CN14, CN15, and CN16 (called "normal" coordinations by Frank and Kasperl). Well-known examples are the cubic and hexagonal Laves phases which have CN12 and CN16, and the 0-tungsten (CrsO) phases which have CN12 and CN14. In the more complicated (often ternary) phases, such as the a phase,2 the Beck phases p3 and R~, the 6 phase,5 and the p p atoms occur with CN12, CN14, CN15, and (except for a) CN16; in many cases several crystallographically independent atoms of one particular CN occur in the asymmetric unit. A large number of independent interatomic distances are found in these complicated phases, varying from 20 in the a phase to 94 in the 6 phase. These distances show a large spread; they vary, for example, from 2.358 to 3.278A in the 6 phase. In our analysis of these distances we found that in each of these compounds every atomic position can be characterized by either one or two radii. The CN12 positions are characterized by a single radius, The higher coordinated positions are characterized by two radii, namely: the CN14 positions by 4 in the direction of the twelve "5-coordinated" ligands3 (called 'minor" by Frank and Kasperl) and by r:, in the direction of the two "6-coordi-nated" ligands (called "major" by Frank and Kasper); the CN15 positions by r15 for the twelve minor and r:, for the three major ligands; the CN16 positions by rlE for the twelve minor and r:, for the four major ligands. We have expressed the experimentally determined interatomic distances in observational equations as the sums of the appropriate pairs of these characteristic radii and the value of these radii have been determined by the method of least Squares. Despite their wide range, the interatomic distances could then be predicted by the sums of these atomic radii with an average deviation in any one compound of 0.06A or less. The results are summarized in Table I. Inspection of the radii thus obtained shows that in the structures in Table I the radii (in A) are given to a first approximation by the simple relationship: Where CN is the coordination number (12, 14, 15, or 16), and A = 1 for major ligands and = 0 for minor ligands. The interaLomic distances can be predicted within about 0.1A by sums of these atomic radii. Another phase belonging in this group with CN12, 14, 15, and 16 is the y phase & B7, in which A is molybdenum or tungsten and B is iron or cobalt. Recently the M%C phase has been refinedE and the observed distances also agree well with those calculated with Eq. [I]. (In the original determination of the structure of W6FeV7 the F$(II)-W(II1) distance was erroneously given as 2.84A, but we have recalculated it fro? the published parameters and found it to b? 2.57i4, in good agreement with the value of 2.6A predicted with Eq. [I.].) Many binary transition alloys are known to crystallize with the simpler structures having "nor-

Jan 1, 1964

By Oliver B. Hopkins

The Peruvian production increased over 3 million barrels from 1933 to 1934—from approximately 13¼ million barrels to over 16¼ million barrels—bringing the cumulative production of the country up to 171 million barrels. Most of this production, as well as most of the increase in 1934, came from La Brea-Parinas Estate, the property of the International Petroleum Co., Limited. In 1932 Peru stood eleventh among the oil-producing countries of the world, but in 1933 her production exceeded that of Trinidad, Argentine and Colombia, which placed her in eighth position. In 1934 Peru's production was exceeded by that of Colombia by about one million barrels, and by that of the Argentine by about 1½ million barrels, thus placing her in tenth position. After several years of relative inactivity in drilling and exploration there was a noticeable increase during 1934 in both of these lines of activity. Oil Fields La Brea-Parinas Estate.—Production on the La Brea-Parinas Estate. reached a significant total of 85,080 bbl. as early as 1891. It increased to over one million barrels in 1912, and to over 10 million barrels in 1929, and in 1934 it reached an all-time high of over 14 million barrels. The total production from 1890 to 1934 was 133,784,609 barrels. Practically all the drilling on the property has been done with cable tools, but during 1934 three strings of rotary tools were introduced. One was a heavy outfit for drilling a deep test and the other two were lighter outfits for deepening wells in the newer section of the field, where the gas pressure was too high to permit safe drilling with standard tools. During 1934 a total of 28,127 ft. was drilled, 66 wells were deepened, and 6 new wells were completed. At the end of the year 2844 wells had been drilled on the Estate, of which 1814 were still productive. The remaining 1030 wells represent abandoned producers or dry holes. The total area that has been productive up to the present time is estimated at 13,369 acres. An interesting article on the various phases of operations of the International Petroleum Co. was written by Arthur Iddings and published in The Oil and Gas Journal (Dec. 27, 1934).

Jan 1, 1935

By J. Jr. Hudy

The objective of this investigation of the Cendrex was to determine the applicability of the X-ray instrument for the measurement of the ash content of coal. Developed by the Dutch State Mines, this instrument is designed to provide ash analysis of any desired coal product with only a 5-minute lag between sample collection and analytical result. The unit could, with limit controls, be used to feed back signals to preset the separating gravity of coal washers, control the ratio of various coals needed to produce an acceptable blend, and permit the sorting of a washed product into two qualities, one which is below and the other which is above a prescribed ash content. This unit can also be used discontinuously for rapid determination of samples of coals taken in the usual manner.

Jan 7, 1968

By E. I. Salkovitz, F. W. von Batchelder

AS Slawson1 and others have already shown, from a geometrical view twinning in the diamond structure may be considered as a reflection across a (111) plane or as a reflection across a (112) plane. An analysis by Ellis and Treuting2 showed that the twinning plane must be the (111) plane, but that a twin might have lateral boundaries along (112) planes. Earlier Slawson1 and Ellis3 had shown that only (111) twinning was present in diamond and germanium respectively. Since an ingot of silicon, 1 in. in diam and 1 1/2 in. long, prepared from Dupont silicon to which 0.2 pct Be had been added was available, it was examined for twinning. The ingot had been cooled slowly from the bottom. A section 1/16 in. thick was ground off from the bottom and then the ingot was sliced vertically through the center. Spectrographic analysis indicated only faint traces of iron and silver, in addition to the beryllium. The sample was first etched with a hot solution of 10 pct NaOH in water.and photographed. Back-reflection Laue patterns were made of the vertical and horizontal sections in the regions designated in Fig. 1. Orientations were obtained for each twin using the Greninger technique. Several regions of the same orientation were found; thus regions A and K were identical, similarly N and P, and C, G, J, and L. Knowing the angles between the traces of the twinning plane on the surface and the specimen axis, the indices of the twinning plane were deduced. In all cases the twinning plane was found to be (111); lateral boundaries, however, were found which were (112) such as the one indicated in Fig. 1. Therefore, as in the case of diamond1 and germanium' only (111) twinning occurs in silicon. We wish to thank Mr. Hino for the use of the ingot as well as for its metallographic preparation. References 1C. B. Slawson: American Mineralogist (1950) 35, p. 193. 2 W. C. Ellis and R. C. Treuting: Trans. AIME (1951) 191, p. 53; Journal of Metals (January 1951). 3W. C. Ellis: Trans. AIME (1950) 188, p. 886; Journal of Metals (June 1950).

Jan 1, 1953

By H. H. Pentz

This paper gives the derivation of a practical formula for the calculation of slopes in seismic reflection prospecting. The derived formula is an approximation and can be used where the slope of the reflecting horizon is less than 250 ft. per 1000 and the depth to the reflecting horizon is greater than 2500 ft. The slope of sediments in oil regions is generally considerably less than 250 ft. per 1000. This is particularly true of the Gulf Coast, with the exception of the salt domes, which usually have the sediments at a greater slope than 260 ft. per 1000. Derivation In Fig. 1, o represents the image of the shot point a. Then the length of the path acb is equal to ob and ae'd is equal to od. In the triangle aob, p is equal to ob, x is equal to , and c is equal to ao. The angle u is the apparent dip of the reflecting horizon. Angle oab is equal to (90" - u). The quantity m is the slope of a line tangent to the curve, defined by equation 1, at the point (p, x). The quantity m' is the slope of the line tangent to the curve at the point (p', 2').

Jan 1, 1940

By H. H. Pentz

This paper gives the derivation of a practical formula for the calculation of slopes in seismic reflection prospecting. The derived formula is an approximation and can be used where the slope of the reflecting horizon is less than 250 ft. per 1000 and the depth to the reflecting horizon is greater than 2500 ft. The slope of sediments in oil regions is generally considerably less than 250 ft. per 1000. This is particularly true of the Gulf Coast, with the exception of the salt domes, which usually have the sediments at a greater slope than 260 ft. per 1000. Derivation In Fig. 1, o represents the image of the shot point a. Then the length of the path acb is equal to ob and ae'd is equal to od. In the triangle aob, p is equal to ob, x is equal to , and c is equal to ao. The angle u is the apparent dip of the reflecting horizon. Angle oab is equal to (90" - u). The quantity m is the slope of a line tangent to the curve, defined by equation 1, at the point (p, x). The quantity m' is the slope of the line tangent to the curve at the point (p', 2').

Jan 1, 1940

By F. M. Doyle-Garner, A. J. Monhemius

Hydrolytic stripping is the process whereby metal ions in a loaded solvent extractant are hydrolyzed by water, typically at 130°C to 200°C (265°F to 392°F). Equilibrium hydrolytic stripping tests were done on Versatic 10 solutions containing various metals, singly and in mixtures. Single solutions of Fe, Ni, Cu, Mg, and Mn precipitated [a]Fe2O3 Ni(OH)2 Cu2O + CuO, Mg(OH)2 and [?]Mn203 respectively, during hydrolytic stripping. Several mixtures containing iron precipitated magnetic spinel ferrites, MFe204. No other combinations formed mixed oxides. It is proposed that the mechanisms for hydrolysis and precipitation of iron in loaded Versatic solutions are similar to those for iron hydrolysis in aqueous solutions. Magnetic interactions between mixed carboxylate complexes are thought to be responsible for the homogenous nucleation of magnetic mixed oxides in preference to single oxides.

Jan 1, 1986