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By C. V. Corless

We are living at a period of the world's history in which social phenomena are on so vast a scale, are of so profoundly soul-searching a nature, and are occurring in such rapid succession in the great world drama in which we are both actors and spectators, that, in our efforts to obtain a rational point of view in relation to them, our minds may fail to discern the simple in the complex and our understanding is liable to become confused or even overwhelmed. To the social student whose: scientific training has convinced him of the truth of the evolutionary law, Natura non facit salium, it is neither the vast scale of the events, their deeply soul-stirring nature, nor their rapid succession that matters so much, as the discovery of the underlying principle or law in accordance with which the disintegration and reintegration, which are the two aspects of social evolution, or indeed of evolution everywhere, are occurring. He is most deeply concerned in seeking an answer to the question: Have we in the present great and perplexing upheavals in human society, whether regarded in Central Europe, in Russia, in Great Britain, or in America, a really new cause at work, or, have we, though on a very large scale, merely new manifestations of the working out of an old principle? When we think of the appalling struggle in Europe, into which the world's greatest exemplar of democracy was finally drawn, no one has any hesitation in admitting that the great conflict was fundamentally a life-and-death struggle for self-preservation and self-propagation on the part of autocracy. The variations we meet with in the statement of the cause of the war arise mainly from differing distances of perspective; but in the last analysis all agree that the autocratic system of political gov ernment, which found its very soul and center in Prussian despotism, was consciously arrayed in a final "world-power-or-downf all" struggle against a love of freedom which was steadily widening and deepening throughout the world, and particularly throughout those parts of the world where this love of freedom and justice hasfound expressionin democratic institutions. It is not irrelevant to our discussion to recall in passing that this most imposing structure ever conceived by the human mind as an instrument of tyranny is lying today an irretrievable mass of ruins, completely over-

Jan 1, 1920

By M. E. Fine, A. A. Hendrickson

The critical resolved shear stress and the strain rate dependence of the .flow stress are reported for Ag base A1 single crystals up to 6 at. pct A1 over a temperature ralzge of 4.1° to 470°K. At room temperature the solid solution strengthening is attributed brinciballv to an increase in the dislocation density on alloying. At 42°K the alloys are relatively stronger because the dislocations widen on alloying and are more difficult to cut. In a previous paper, the authors reported the characteristics of strain aging in Ag base A1 alloys.' The variation of the magnitude of the strain-aging yield drops on aging time, aluminum content, and testing temperature strongly indicated that the phenomenon is due to the Suzuki mechanism. In the present paper, the critical resolved shear stress (CRSS) and the strain rate dependence of the flow stress are reported for Ag base A1 single crystals as functions of testing temperature (4.2" to 470") and A1 content (0 to 6 at. pct). Observations on the substructure and measurements of the effect of crystal growth rate are also given. The experimental re- sults appear explainable considering that aluminum additions increase the dislocation density and dislocation width. EXPERIMENTAL METHOD The methods of specimen preparation and tensile testing were described previously.' Briefly, single crystals were grown from the melt in a vacuum (1 x lom5 mm Hg), shaped into tensile samples by a combination of abrading and acid etching, annealed at 850°C in a vacuum (1 x 10" mm &Z) for several days, and furnace cooled to 200'. The testing was done on a model TM Instron using friction grips and a strain rate of about 5 x 106 per sec unless otherwise noted. The various testing temperatures were obtained by immersing the specimens in the following media: 1) 4.2': liquid helium using the apparatus of G. Byrne;' 2) 77°K: liquid nitrogen; 3) 200"K: dry ice and acetone; 4) 415' K: ethylene glycol; 5) 460' \ to 480' : molten Stanalax. In the determination of the CRSS above 296' K, a ratio method was used; the crystals were strained initially at the higher temperature, 0.1 pct shear strain, and then tested at 296' . The ratio of the flow stress between the two temperatures was then multiplied by the average CRSS at 296' K to obtain the value of the CRSS at the high temperature. (The test at 296' showed a yield point resulting from strain aging; the flow stress at 296' K was taken as the lower yield stress.) The ratio method, we believe, is more accurate than using different crystals since

Jan 1, 1962

By R. W. Fountain, M. Korchynsky

The precipitation phenomena occurring in cobalt-tantalum alloys have been investigated in the temperature range frm 500" to 1050°C by correlating the results of metallographic, X-ray, micro-and macrohardness, and electrical resistivity studies. The property andmacrohardness,changes were found to depend on 1) general precipitation, and 2) lamellar precipitation. Two new intermetallic phases have been identified: 1) a Co3Ta, a metastable ordered face-centered-cubic compound, and 2) a stable ß Co3Ta phase of hexagonal structure. In addition, the previously reported Co2Ta phase was found to exist in two allotropic modifications: the hexagonal MgZn,-type and the cubic MgCu2-type Laves phases. SINCE a large variety of structures can result as a consequence of the decomposition of a solid solution, predictions on the nature of property changes are difficult, if not impossible, to make. For any rational attempt to correlate properties and structures of a precipitation-hardenable alloy, a detailed understanding of the kinetics of decomposition and morphology of phase separation, as well as knowledge of phase relationships, appears to be prerequisite. Information of this type has been accumulated in the past for many alloy systems, both of theoretical and pastforpractical importance.1,2 Although the presence of intermetallic compounds has been reported in cobalt-base alloys,3 the amount of published information on precipitation-hardenable cobalt-base systems is very limited. A survey of the binary phase diagrams of cobalt indicates that cobalt-tantalum alloys might be of interest as typical of other cobalt-base systems in which Laves phases of the A,B type can be precipitated from solid solution. The present work has been undertaken, therefore, to study the kinetics and morphology of the precipitation reaction in this system and to establish a base for a correlation between the structural aspects and properties in this class of alloys. PREVIOUS WORK The only available phase diagram of the cobalt-tantalum system is based on the work of Koster and Mulfinger. According to these authors, the maximum solubility of tantalum in cobalt is about 13 pct (at 1275°C) and. less than 7 pct at room temperature. Tantalum additions lower the temperature of allotropic transformation of cobalt (about 420°C), and at 7 pct Ta, the high-temperature face-centered-cubic modification (ß cobalt) is retained at room temperature. The precipitating phase was originally designated as Co5Ta2 compound (55.2 pct Ta, about 1550°C melting point), but subsequent investigations by wallbaum5" identified this constituent as the A,B-type Laves phase. Wallbaum's data indicate that there are two modifications of this intermetallic compound: one richer in cobalt (Co2.2 Tao.8)of the hexagonal MgNi, type; and another of a higher tantalum content (Co2Ta) of the cubic MgCu, type. On the other hand, Elliott7 found that the cobalt-rich alloy (CO2.10,Tao.~l) was predominantly the cubic MgCu, type at 800°C and a mixture of both the MgCu2 and the hexagonal MgZn,-type Laves phases at 1000°C. At 1200°C, Elliott found only the MgZn, type while at 1400°C, he observed only the MgCu2 type. At the stoichiometric composition, Co2Ta, Elliott reported only the cubic MgCu2-type Laves phase in the temperature range of 600oto 1600°C. The precipitation of the cobalt-tantalum intermetallic compound is accompanied by a marked increase in hardness. According to Koster's4 data, the Brinell hardness of an 8 pct Ta-Co alloy increases from 230 to 340 upon short-time aging at 800°C. EXPERIMENTAL PROCEDURE The binary cobalt-tantalum alloys investigated contained 5, 10, and 15 pct Ta. The range of tantalum additions was thus slightly broader than the reported minimum and maximum solid solubility limits of tantalum in cobalt (7 and 13 pct, respectively)4 The alloys were vacuum-induction melted in a magnesia crucible using cobalt rondelles and technically pure tantalum sheet as raw materials. Deoxidation of the melt was accomplished with carbon, and the chemical analysis of the alloys is given in Table I. The effect of isothermal aging treatments on the progress of precipitation was studied on samples cut from cast ingots. These samples were solution treated for 2 hr at 1250°C and water-quenched. Aging was conducted in the temperature range from 500" to 1050°C for periods between 15 min and 1000 hr and followed by water-quenching. To prevent contamination from the atmosphere, all samples were sealed in evacuated Vycor or quartz tubes for heat-treatments. For solution treatment, argon at 0.2 atmospheric pressure was introduced prior to sealing of the capsule to prevent collapse at high temperature, and titanium sponge was placed at one end of the capsule to act as a getter. MACROHARDNESS The effect of aging on Vickers hardness (Dph) of

Jan 1, 1960

By F. C. Bond

SIZE of grinding media is one of the principal factors affecting efficiency and capacity of tumbling-type grinding mills. It is best determined for any particular installation by lengthy plant tests with carefully kept records. However, a method of calculating the proper sizes, based on correct theoretical principles and tested by experience, can be very helpful, both for new installations and for guiding existing operations. As a general principle, the proper size of the make-up grinding balls added to an operating mill is the size that will just break the largest feed particles. If the balls are too large the number of breaking contacts will be reduced and grinding capacity will suffer. Moreover, the amount of extreme fines produced by each contact will be increased, and size distribution of the ground product may be adversely affected. If the balls added are too small, grinding efficiency is decreased by wasted contacts that are too weak to break the particles nipped; these largest particles are gradually worn down in the mill by the progressive breakage of corners and edges. Ball rationing is the regular addition of make-up balls of more than one size. The largest balls added are aimed at the largest and hardest particles. However, the contacts are governed entirely by chance, and the probability of inefficient contacts of large balls with small particles, and of small balls with large particles, is as great as the desired contact of large balls with large particles. Ball rationing should be considered an adjunct or secondary modification of the principle of selecting the make-up ball size to break the largest particle present. Empirical Equation In 19521,2 the author presented the following emerical equation for the make-up ball size: B - ball, rod, or pebble diameter in inches. F = size in microns 80 pct of new feed passes. Wi - work index at the feed size F. Cs - percentage of mill critical speed. S — specific gravity of material being ground. D == mill diameter in feet inside liners. K - 200 for balls, 300 for rods, 100 for silica pebbles. Eq. 1 was derived by selecting the factors that apparently should influence make-up ball size selection and by considering plant experience with each factor. Even though Eq. 1 is completely empirical, it has been generally successful in selecting the proper size of make-up balls for specific operations. But an equation based on theoretical considerations should be used with more confidence and have wider application. The theoretical influence of each of the governing factors listed under Eq. 1 was accordingly considered in detail, as described below, and a theoretical equation for make-up ball sizes was derived. Derivation of Theoretical Equation Ball Size and Feed Size: The basis of this analysis is that the largest ball in a mill should be just sufficient to break the largest feed particle into several pieces, excluding occasional pieces of tramp oversize. In this article the size F which 80 pct passes is considered the criterion of the effective maximum particle feed size. The smallest dimension of the largest particles present controls their breaking strength. This dimension is approximately equal to F. As a starting point for the analysis it is assumed that a 1-in. steel ball will effectively grind material with 80 pct passing 1 mm, or with F- 1000µ or about 16 mesh. The breaking force exerted by a ball varies with its weight, or as the cube of its diameter R. The force in pounds per square inch required to break a particle varies as its cross-sectional area, or as its diameter squared. It follows that when a 1-in. ball breaks a 1-mm particle, a 2-in. ball will break a 4-mm particle, and a 3-in. ball a 9-mm particle. This is in accordance with practical experience, as well as being theoretically correct. Confirmation of this reasoning is supplied by the Third Theory of Comminution," which states that the work necessary to break a particle of diameter F varies as F. Since work equals force times distance, and the distance of deformation before breaka4e varies as F it follolvs that the breaking force should vary as F½ These relationships are expressed in Table I, with a 1-in. ball representing one unit of force and breaking a 1-mm particle. This establishes theoretically the general rule used in Eq. 1 that the ball size should vary as the square root of the particle size to be broken. Ball Size and Work Index: The work input W required per ton" varies as the work index Wi, and the

Jan 1, 1959

By S. G. Cupschalk, J. J. Wert, R. A. Buchanan

The uniaxial deformation of thermally ordered and disordered polycrystalline Cu3Pt was studied by means of the X-ray line - broadening analysis according to Warren and Averbach and the extension of this analysis to ordered fcc materials by Mikkola and Cohen. Because of the heat treatment history, extinction had a pronounced effect on the X-ray spectra of ordered and disordered C%Pt at small plastic strains. After an appropriate correction for extinction, the long-range order in thermally ordered ChPt was found to decrease at a slow constant rate with plastic strain. Furthermore, the antiphase domain probability increased at a constant rate to 17.5 pct strain. The effective particle size behavior indicated that the stacking fault energy is lower in ordered than in disordered Cu3Pt. Analysis of the stress-strain curves shouled that ordered Cuzt has a slightly lower yield Point but a much higher work-hardening rate than disordered Cu3Pt. THE presence of long-range order in a solid-solution alloy has a marked effect on its mechanical properties. While this effect has been known qualitatively for many years, it was not until recently that detailed investigations have been performed to determine the exact role long-range order plays in this strengthening mechanism. The development of an advanced, quantitative. X-ray diffraction analysis by Warren and Averbachl and the extension of this analysis to the L1, type super lattice by Mikkola and cohen2 have greatly accelerated research in this field. The research reported in this paper consisted of two primary phases. The first phase was to determine the effect of long-range order on the tensile properties of polycrystalline Cu3Pt. This objective was accomplished by comparing the stress-strain behavior of thermally ordered CusPt to that of thermally disordered CusPt. The second phase of the research was to determine the difference between the atomic arrangements in thermally ordered and thermally disordered Cu3Pt as a function of uniaxial deformation and thereby gain a deeper insight into the mechanism by which long-range order affects the tensile properties. This second objective was accomplished by applying the Warren-Averbach method of peak profile analysis to the X-ray diffraction patterns obtained from ordered and disordered Cu3Pt after given amounts of uniaxial deformation. EXPERIMENTAL PROCEDURE The Cu3Pt was prepared by vacuum melting and casting. After a homogenization anneal, the ingot was cold-rolled to sheet form. Two tensile specimens with gage sections of 2.50 by 0.500 by 0.115 in. were carefully machined from the sheet. The specimens were polished with a final step of 600-grit paper to insure smooth diffracting surfaces. Finally, one specimen was heat-treated to yield an average grain diameter of 0.016 mm and an initial degree of long-range order, S, of 0.825. The other specimen was water-quenched from above the critical temperature, 645"C, to yield an average grain diameter of 0.017 mm and zero long-range order. The heat treatment history of each specimen is shown in Table I. The tensile tests were performed utilizing a Research Incorporated Model 900.95 Materials Testing System. This unit employs a closed-loop feedback system which maintains a constant strain rate through an extensometer clipped to the gage section of the tensile specimen. A strain rate of 1.32 i0.02 x 10"4 sec-' was employed in testing both specimens. In the X-ray diffraction analysis, a General Electric XRD-5 diffractometer equipped with a pulse-height analyzer set for 90 pct efficiency was employed. The goniometer speed selected was 0.2 deg, 20, per min. Filtered Cu radiation was used for all peaks and all peaks were chart-recorded. Because of nonuni-form grain size. it was necessary to spin the specimens during X-ray analysis in order to obtain reproducible integrated intensities. The spinning rate was 2000 i100 rpm. The application of the Warren-Averbach method of peak broadening analysis to a diffraction pattern is very time consuming if done manually. In this research, the calculations involved were performed with the aid of a computer program by wagner.3 As reported by Wagner, the program is written in Fortran TV computer language. It was modified to Fortran I1 so as to be handled by the IBM 7072 computer at Van-derbilt University. In the X-ray diffraction analysis of uniaxially deformed Cu3Pt, the 100, 200. 400. 111, and 222 reflections were recorded from the initially ordered sample after 'plastic strains of 3.0, 6.0, 9.0, 12.0,

Jan 1, 1970

By W. Bonfield

A study has been made of the dislocation substructures produced in hot-pressed beryllium specimens strained to various levels in the range from 800 x 10-6 In. pev in. to fracture. A number of distinctive dislocation configurations were observed in this region which had not been noted at lower levels of strain. These included dislocation-dislocation interactions to form networks, dislocation "walls", subgrain boundaries and complex arrays, interactions between dislocations and large beryllium oxide particles, and the generation of dislocations from certain particles. The nature of these differences in substructure and their relation to the stress-strain characteristics of polycrystalline beryllium are discussed. In a previous study1 of the plasticity of commercial-purity, hot-pressed beryllium a transition was found in the deformation characteristics in the mi-crostrain region. The initial plastic deformation could be represented by a parabolic stress-strain equation, but above a critical stress there was a complete departure from this relation and a reduction in the strain-hardening rate. The dislocation configurations produced by various levels of micro-strain in this region were examined by transmission electron microscopy and a general correlation was established between the observed transition in deformation characteristics and the dislocation structure of the material. The two stages in the micro-strain region distinguished in these experiments were designated as Stage A' and Stage B'. Stage A' type deformation generally was noted up to a plastic strain of -80 x 10"6 in. per in. and Stage B' type from -80 x 10-6 to -800 x 10'6 in. per in. The discovery of two stages in the microstrain region naturally posed pertinent questions as to the existence of any further distinct stages in the subsequent plastic deformation. The purpose of this paper is to present a study of the dislocation configurations produced in similar beryllium specimens strained to various levels in the range from -800 x 10 in. per in. to fracture and to discuss the relation between substructure and the stress-strain characteristics. It is concluded that this region of strain can be considered as a distinct stage in the plastic deformation of polycrystalline beryllium. Tensile specimens of gage length 1 in. and cross section 0.18 by 0.06 in. were prepared from commercial-purity, hot-pressed QMV beryllium and then annealed at 1100°C for 2 hr. 2 followed by a careful chemical polishing procedure.3 The specimens were strained at a constant rate to various levels of strain in the range from -800 x 10-6 in. per in. to fracture (at 0.5 to 2 pct elongation), using the Tuckerman strain-gage technique1 to measure plastic and total strain. Thin foils were obtained from the strained and fractured specimens by chemical polishing3 and were examined using an RCA-EMU 3 electron microscope. Considerable care waS taken to avoid both accidental deformation during the preparation of the thin foils and excessive heating during their examination. Selected-area diffraction patterns were determined for each micrograph. Tilting experiments were also performed whenever appropriate to establish the dislocation zero-contrast position and hence determine the Burgers vector. This operation was sometimes not possible due to the rapid contamination of the foils which occurred in the electron microscope. RESULTS AND DISCUSSION To enable the distinctions between the dislocation arrays at high and low strain levels to be adequately made, the main characteristics of Stage A' and Stage B' deformation are briefly reviewed. 1) Stage A'. In the annealed starting condition there was a variable density (5 x 107 to 3 x 10' cm per cu cm) of isolated dislocations within a grain. The initial deformation in a tensile specimen was heterogeneous, with the dislocation density increasing in a few grains to 5 x 10g to 1.5 x 101° cm per cu cm. The deformation occurred exclusively on the basal plane by the movement of one or more 1/3 (1130) type dislocation systems. The dislocations were long and regular in form and nearly all the intersections exhibited a simple four-point node configuration. No interactions between glide dislocations and beryllium oxide particles were observed. 2) Stage B. In Stage B' there was a large increase in the number of grains exhibiting dislocation movement and also a change in the nature of the deformation, in which jogged dislocations and elongated loops became the characteristic feature. The splitting up of the elongated loops into smaller loops and the possibility of source action from the re-

Jan 1, 1965

By R. H. Maes, R. E. de Strycker, J. J. Jacobs

A simple method, based upow density measurements, has been perfected in order to determine the critical temperature of liquid miscibility gaps. Applied to the Pb-Cu system, it yielded a value of 980"C for the critical tempevature of the miscibility gap in this system. In the Pb-Cu-As system, the immiscibility between lead and coppev evolves towards a miscibility gap be-tween lead and copper arsenides; the liquation temperatures were determined joy different avsenic contents and values up to 1065°C were found. Combining these results with those given by the clzemical analysis of liquid samples taken at dqj.event temperatures, it has been possible to make a cowzplete determination of the liquid miscibility gap in this ternary system. In the Pb-Cu-Fe-As system, a ternary miscibility gap has been discovered; for some compositions, the molten and slowly cooled alloys separated into three layers: an Fe-As alloy, a Cu-As alloy, and a lead-rich layer. ThE Pb-Cu-Fe-As system is of interest for the study of the behavior of speiss or arsenical alloys in the lead blast furnace. The speisses produced in lead metallurgy generally have complex compositions, but they may be considered, in a simplified way, as a mixture of copper, iron, nickel, and cobalt arsenides; there is often an excess of metallic constituants, and lead is also present. Speisses liquate from lead at various temperatures according to their composition; according to industrial experience, iron speisses are already distinctly separated from lead bullion at temperatures of the order of 1100°C, whereas copper speisses only begin to liquate from lead at much lower temperatures, near their solidification points, which were never accurately determined until now. Besides these considerations of practical interest, the present study is of importance for the knowledge of liquid miscibility gaps. Particularly the data of the literature about critical temperatures of liquation are incomplete and present sometimes considerable disparities; a method has been perfected in the present work to determine these temperatures with accuracy. MISCIBILITY GAP OF THE LEAD-COPPER SYSTEM Review of Literature. The generally admitted outline of the Pb-Cu equilibrium diagram is shown by Fig. 1. This figure, with its numerical indications, is taken from the review of Hansen and ~nderko;' compositions are given in weight percent, as will be the case in the remainder of this paper. Between 36 and 87 pct Pb, Pb-Cu alloys separate into two layers, in the liquid state. The critical temperature of liquation has been much disputed in earlier studies, where values up to 1500°C were claimed; but a reliable study of ~ohnen,' based upon differential thermal analysis, gave a value of 990°C; this rather low value was verified by a recent study of Schiirmann and Kaune? based upon thermodynamical properties of the Pb-Cu alloys, which predicted a value of 1002°C. Liquid miscibility gaps were also studied by means of chemical analyses. Satisfactory results were generally obtained with the method consisting in taking samples of the two liquid layers in equilibrium and submitting them to chemical analysis; however, this method becomes delicate near the critical temperature. With this technique, Friedrich and waehlerts ob-

Jan 1, 1968

By ALEX. S. THOMAS

HOWEVER good a furnace may be in regard to design, etc., or however excellent in the quality of the gas used, a suitable heat for the successful working of the metal cannot be obtained unless the melt be coated with a proper quantity of slag. This coating may be excessive or it may be deficient in quantity. The right degree of heat is the essential condition of successful working, for the quality of the steel made is never very good when the metal is allowed to simmer in the furnace for an excessive period, and this heat cannot be obtained if the metal is not protected by a proper covering of slag. This is not only to prevent the metal being over-oxidized and wasted, but also to prevent the metal being chilled when exposed with only a thin covering of slag. The slag may be obtained in either of two ways : 1, naturally, by the presence of sufficient silicon in the iron used, to unite with iron oxide to form a staple slag ; or, 2, by the addition of slag or free silica. In the first case the slag is formed naturally by the action of the oxygen in the flame - i.e., the oxidizing atmosphere of the furnace-on the silicon in the metal when melting. The charge then melts, as it is termed, "thick," and protects the banks from being cut. If too much silicon be present, however, and an excessive quantity of slag be formed, it will be found to be rather infusible, and unless care be taken to add the oxides quickly and follow the furnace up-thus rendering the slag more fusible by the extra iron oxide-the furnace bottom is liable to be pulled up. In such cases the author has frequently been able to warn

Nov 1, 1906

By John P. Bryant

Plant nutrients are obtained by plants from both the air and the soil. Carbon dioxide, a gaseous form of carbon and oxygen, supplies the carbon which usually makes up 50% or more of plant structure. Plants are capable of absorbing carbon dioxide directly from the air. Most of this nutrient comes from the air, although some carbon dioxide is absorbed by soil water and taken into the plant as liquid. Growing plants use more water than any other substance. Plant nutrients in the soil dissolve in soil water; soil water entering the plant carries nutrients into the plant structure. Water is then given off into the air as the plant breathes or transpires. The inorganic or mineral portion of the nutrients which plants require comes from the soil. Inorganic or mineral composition of plants is usually less than 5% of their weight, and this mineral requirement, usually lacking in the soil, must be provided by fertilizers. Proper fertilization of a soil to improve its mineral level and productivity is the basis for the fertilizer industry (Thomas, 1960). There are 13 essential plant nutrients which often must be added to soils or plants and are generally considered as fertilizer minerals. These nutrients are divided into the categories: primary minerals (nitrogen, phosphorus, potassium); secondary minerals (calcium, magnesium, sulfur); and micro or trace minerals (boron, iron, manganese, copper, zinc, molybdenum, chlorine). Further, cobalt is often added to fertilizers. Although it is not considered to be an essential plant nutrient, it is essential to animal health and is often applied to forages as a fertilizer constituent. One point of major significance to the fertilizer industry is that not all nutrient carriers supply that nutrient in a chemical form which will be available to the plant. Thus, a product which may be considered a fertilizer mineral may require substantial processing or treatment before it becomes useful as a nutrient carrier. Fertilizer Industry Scope Until about 1900 demands for higher crop yields were met simply by bringing new agricultural lands into cultivation. Since that time great progress has been made in increasing yields through fertilization and improved varieties and cultural practices. The importance of the fertilizer industry to the economy and welfare of the U.S. is widely recognized. [Fig. 1] illustrates the relationship of lime and fertilizers to crop yields. In terms of tons of fertilizer products, the growth of the industry has been phenomenal, particularly between 1950 and 1970. Table 1 shows the increase in fertilizer usage. Primary Plant Nutrients in Fertilizers Primary minerals (nitrogen, phosphorus, potassium) are designated as such because of their significance to plant growth. Practically all soils are deficient in both nitrogen and phosphorus, and most of them are also deficient in potassium. Consequently, these nutrients

Jan 1, 1975

By G. W. Binkley, G. K. Dumbauld, F. A. Brooks, B. E. Morgan

In recent years, oil well cementing compositions have been developed with low densities, controlled set strengths, and satisfactory thickening times. With the introduction of the permanent-type well completion method for cementing wells, another property—that of rate of filtration or water loss to permeable formations— has become important. Laboratory data show that cement slurries prepared with oil, water, bentonite, and calcium lignosulfonate possess satisfactory thickening times, strengths, and filtration properties for primary cementing of casing and for squeeze cementing with the permanent-type well completion technique. Cementing compositions have been prepared with oil-in-water emulsions varying in composition from 60 cc water and 20 cc oil per 100 gm cement to 90 cc water and 45 cc oil per 100 gm cement. These compositions have contained from 0.4 to 5.0 per cent calcium lignosulfonate by weight of dry cement. Slurries prepared from these compositions weigh 11.4 to 13.1 lb/ga1 and have filtration rates of from 10 cc to approximately 100 cc in 30-min API tests at room temperature. The unfiltered emulsion cements develop one-day tensile strengths of 60 to 220 psi; and the filtered mass sets to tensile strengths of 60 to 150 psi in 12 hours and develops strengths of 320 to 515 psi in seven days when cured at 125° F. Field experience gained from 13 field mixing jobs demonstrates the utility of the emulsion cement for permanent-type squeeze cementing operations. INTRODUCTION In recent years, research in oil well cementing composition has been directed toward the development of cements having low densities, controlled set strengths, satisfactory thickening times, and low rates of water loss by filtration. Two well cementing compositions that have been developed with these properties are the modified cements containing, respectively, 12 and 25 per cent bentonite clay and various concentrations of calcium lignosulfonate1,2 In a search for other ways to incorporate these characteristics in a cementing composition, consideration was given to the rheological properties of oil-emulsion drilling fluids. Many of the desirable properties observed in oil-emulsion drilling fluids are equally advantageous in a cementing composition. For example, low water loss by filtration and low density, which are inherent characteristics of these oil-in-water emulsions, are desirable for many oil well cementing operations. Furthermore, oil-emulsion slurries have lubricating properties similar to those of oil-emulsion muds, a factor which should provide ease of rotation of casing during primary cementing operations. The properties of lubrication and low filtration may be of special value in both primary and squeeze cementing operations encountered in slim-hole drilling. Studies in the preparation of oil emulsion systems have pointed out the need for violent agitation in order to disperse the oil into the water phase. It was thought, therefore,

Jan 1, 1957

By Thomas MacFarlane

AMONG the industrial enterprises which have, from time to time, been undertaken in our Dominion, few have been more uniformly unsuccessful than those which have had for their object the develop ment of our mineral resources. These resources hare not been re garded as insignificant. On the contrary, it is supposed that we possess in our ore deposits something more than mere points of mineralogical interest. Some people are enthusiastic enough to be lieve that our mineral wealth will yet occasion the establishment in our backwoods of happy and industrious communities, causing, in fact, our wilderness to blossom as the rose. These enthusiasts do not shut their eyes to the serious obstacles which at every stage in terfere with the carrying out of mining enterprises in this country, and which tempt one to believe that no such enterprise can ever be conducted to a desirable end, but they entertain the conviction that as our capitalists, miners, and technologists reach the years of discretion, and handle our mines in an economical, vigorous, and judicious manner, and as our statesmen become alive to the necessity of fostering, without extremely protecting, our metallurgical indus tries, mines and furnaces will gradually prosper, and so develop as to become a tower of strength to our agricultural, manufacturing, and mercantile interests. The fact that our past experience does not generally justify such glowing anticipations makes one all the more anxious to put on record the history of a successful mine, such as the Silver Islet has, on the whole, been. My connection with its discovery and early development was a very intimate one, and I propose in this paper to sketch its history and character, and sum up the amount of silver it has so far yielded. An additional reason for the appearance of this paper is that the Transactions of the Institute contain only a few references to the Silver Islet Mine. Although this mine is reported successful, we have, of course, no guarantee that it will not fall a victim to the same influences which have

Jan 1, 1880

RichaRd PeaRce, Argo, Colo.: This contribution upon the very interesting subject of the origin of the gold of certain lode-formations offers many subjects for thonghtful consideration. The explanation, for instance, of the perplexing features of thin lava dikes seems to me to be in harmony with facts as I have myself observed them elsewhere. At Marshall basin, near Telluride, Colorado, there is an extensive lava-flow. The material of this formation contains a large proportion of fragments of foreign matter in the form of angular pieces of rock. The latter show no signs of having undergone metamorphism, such as would be expected to be due to the direct effects of heat; and the evidence in this particular case would certainly lead me to suppose that the flow was due to causes analogous to those suggested by Mr. Rickard. It was, I believe, a moving mass of material, having a temperatrire considerably below the actual melting-point of the rock of which it is composed. In regard to the theory which the author has built up from the existence of the iodide of gold in sea water, I cannot consider it untenable ; but I would put the question whether any investigations have been made with a view to determining whether gold and silver occur in the beds of rock-salt, formed, as is generally allowed, by the evaporation of bodies of salt water. At Stassfurt, in Germany, there is a very remarkable series of alternating beds of rock-salt and anhydrite, the uppermost members of which are covered with deposits of potash salts. The question occurs to me, why should not gold and silver have been discovered in these deposits? Iodine and bromine, I believe, have been found in the salts last deposited by

Jan 1, 1894

By Richard S. McCaffery, Clarence H. Lorig, Joseph F. Oesterle, Ira N. Goff, Oscar O. Fritsche

This paper is the report of an investigation to determine the relations between the viscosity, temperature and composition of that portion of the silica-alumina-lime-magnesia system(l) within which blast-furnace slags are found. The work reported in this paper was made possible by a grant of funds from Engineering Foundation. It is a part of a project, the determination of properties and structure of iron blast-furnace slags, upon which the laboratories of the University of Wisconsin have been at work for some years. Three papers have been published, which have marked the progress of the study of iron blast-furnace slags at Wisconsin. The first,(2) Desul-furizing Power of Iron Blast-furnace Slags, discussed the solubility of sulfur in slags that contained no magnesia and discussed the viscosity. The second, (3) The Constitution of Iron Blast-furnace Slags, developed the constitutions of slags in the four-component system, silica-alumina-lime-magnesia, and pointed out an explanation of slag structure. Composition of Iron Blast-furnace Slags,(l) which was the third paper, gave a method of calculating the percentages of the various compounds present in slags when the amount of oxide was given and also an interpretation of quaternary equilibrium. Illustrations were given of the mineral composition of blast-furnace slags and some applications of composition results were shown. Because of their relative ease of measurement, the viscosity-temperature relation for slags was selected as a factor which would be useful in correlating the physical properties of molten slags to furnace operation. With this in mind the viscosities of slags whose compositions are in that portion of the quaternary system, silica-alumina-lime-magnesia, in which blast-furnace slags occur, were thoroughly investigated.

Jan 1, 1932

By C. Cronquist

Since April, 1962, Shell Oil Co. has operated a peripheral line-drive waterflood of the 10.750-ft lower Tuscaloosa (Cretaceous) Denkman sand in the Little Creek field. Located in southwestern Mississippi in the lower Tuscaloosa trend, the field was discovered by Shell in Jan., 1958. Among the largest in the trend, the accumulation is controlled stratigraphically and occurs in an extensive series of alluvial-point bar deposits across a nose that dips gently to the south. The crude oil is 39" API gravity and was highly undersaturated at initial conditions. Early production behavior indicated a depletion drive with slight water influx; primary recovery wm estimated to be 25 million bbl, or 24.5 percent of stock-tank oil originally in place. A.s a result of a favorable mobility ratio and remarkably uniform rock properties, the volumetric sweep eficiency in the waterflood has exceeded 90 percent. Despite the high connate water saturation (56 percent), the displacement efficiency by water injection has been quite efficient, contrary to traditional concepts. Based on observed field flood-out performance, ultimate recovery is calculated to be 46 million bbl. As anticipated, the production rate began declining during 1964 due to a continu ing reducrion in the number of producing wells as flood fronts advanced across the field. Cumulative recovery as of Jan., 1968, was 44.8 million bbl; waterflood operations ~hould be complete by 1970. Introduction Most waterfloods described in reservoir engineering literature involve pattern operations, the most common of which is the five-spot pattern. Only occasiona'lly are linear drives described, even though there probably are increasing numbers being put into operation. Increasing use of linear floods may reflect the accelerating trend towards early application of fluid-injection programs when linear drives are more efficient, as was the case at Little Creek. However. the Little Creek operation is unusual in several respects. It is one of a few successful waterfloods conducted in sands with connate water saturations approaching 60 percent, and it is among the deepest successful water-floods being operated anywhere. Development The Little Creek field was discovered in Jan., 1958, in the lower Tuscaloosa trend in southwestern Mississippi (Fig. 1). The discovery well, Shell-Lemann No. 1, was drilled on a seismic closure about 2 miles southeast of lower Tuscaloosa production at Sweetwater. The well was completed in the Denkman sand at 10,752 ft, and on initial potential it flowed 588 BOPD of 39" API crude on a %+-in. choke; psi was 730 and GOR was 442:l. Development proceeded rapidly on 40-acre spacing, and by the end of 1958 the field was producing approximately 9,100 B/D from 56 wells. Almost all this production came from the northern half of the field. The southern part was discovered in Nov., 1958, at a location almost 2 miles from previously established production. Subsequent drilling established an apparent conneotion about half a mile wide between the twd areas. Development of the field was practically complete by 1961 with the drilling of 155 producers and 35 dry holes. Some early wells were completed open hole but moslt are completed with casing cemented through the productive interval and perforated for production. Geology The lower Tuscaloosa structure in this area is a north-south nose with maximum dips of about 2" on the flanks. There is no discernible faulting at the producing horizon. Productive limits of the field are shown in Fig. 2, which is contoured on a marker just above the main productive zone. A common water level at 10,415 ft subsea was logged at both the northwest and southeast ends of the field. There is a gross oil column of nearly 100 ft (Fig. 2). Since there is less than 40 ft of closure, it is apparent that bhe accumubtion is controlled stratigraphically, being limited by a sand pinch-out across the creslt of the nose. The total produc-

Jan 1, 1969

By W. A. Ver Wiebe

The year 1939 in Kansas, with a production of 57,944,300 bbl. from 19,669 wells, shows a slight recession from the peak of oil production reached the previous year, when slightly over 59,000,000 bbl. of oil was marketed. The previous peak had been reached in 1917 with 45,451,000 bbl. marketed. Another still earlier peak had been reached in 1904, when slightly less than 5,000,000 bbl. was produced and sold. The production of gas probably reached a new peak during 1939 with a total of over 69 billion cubic feet. Between the peak of the year 1908, when over 80 billion cu. ft. was produced, and that of 1939 the production dropped to 16 billion cu. ft., in the year 1921. During the year 1458 wells were drilled. This figure is somewhat lower than that given in several trade journals, because it does not include wells that were deepened or recompleted in a different geological horizon. Nearly 75 per cent (1029) of the total number of wells were completed as commercial oil wells (824 in western and 205 in eastern Kansas). The commercial gas wells completed number 71, of which 24 are in eastern Kansas and 47 in western Kansas. The remaining completions include 154 dry holes in eastern and 204 dry holes in western Kansas. Based on daily potential capacity the new discoveries of the year accounted for a cumulative initial production of 264,000 bbl. in eastern and 1,158,827 bbl. in western Kansas. It is interesting in this connection to note that the number of wells completed in the state rose gradually to a first peak in 1904, when 2782 were drilled. The number dropped off rapidly to 368 three years later, but rose to the second and highest peak in 1918, when 4671 wells were completed. In the period between 1904 and 1912 more gas wells than oil wells were completed. Between the high peak of 1918 and the somewhat lower peak of 1937, the low point was reached during 1931 with the completion of only 470 wells. In the matter of new pools discovered, Kansas again ranks high. The exact number depends somewhat upon the interpretation of a "new" area—whether it should be called a new pool or a long extension of an older pool. In some places this determination cannot be made until more wells are drilled within the area. Therefore, the figures given

Jan 1, 1940

By Parke A. Dickey, R. Fettke

Drilling activity during 1944 increased considerably in the oil fields and slightly in the shallow gas fields of western Pennsylvania. The number of deep tests (middle Devonian or deeper) completed during 1944 was the same as in 1943 and did not result in discoveries of additional reserves of natural gas or oil. Thus far no commercial oil production has been obtained from sands below the Upper Devonian in Pennsylvania. As a result of the lack of new discoveries, oil production in nearly all of the producing areas in the entire Pennsylvania grade region declined 10 to 11 per cent. Stocks of Pennsylvania Oil The Peilnsylvania grade crude-oil stocks in storage on January 1943 were 2,479,000 bbl. In January 1944 crude stocks totaled 1,846,000 bbl., and during 1944 the stocks of Pennsylvania grade crude declined to a year-ending balance of 1,617,000 bbl. Nearly all of this oil is "unavailable for use," representing pipe-line fill, tank bottoms and limited working inventories at the refineries. The storage of Pennsylvania oil has declined to a point where little or no available crude oil is currently in storage. Prices The posted price of Pennsylvania oil remained constant during 1944; however, on Rug. I, 1944, the wartime Government subsidy was instituted at a rate of 75¢ per barrel. The average price in the Bradford area, including the subsidy, was $3.31 per barrel. New Technical Developments The Pennsylvania Grade Crude Oil Association started a rather ambitious program of research in production fundamentals and technology during 1944. Several well-qualified engineers have been employed and a laboratory is to be equipped at Bradford. The group will investigate, in cooperation with the American Petroleum Institute, the possibilities of bacteria as agents in oil recovery, and undertake other studies of both a fundamental and an applied nature. In cooperation with the Pennsylvania State College, the Research Group worked out a method of measuring water-intake rates in different strata. The method involves injecting salt water down a string of tubing and fresh water down the annulus, determining the location of the interface electrically, and measuring the input rates above and below the interface. The United States Bureau of Mines, in cooperation with oil companies of the Venango district, developed a simple gas-lift tubing string, which is operating successfully in some 20 wells. This device uses the air-gas mixture produced with the oil to lift it by the usual gas-lift principles. The Northern Ordnance Co. is experimenting with a chamber lift device that expels the oil in an unbroken column. These devices hold considerable promise

Jan 1, 1945

By A. J. Opinsky, J. L. Orehotsky, L. L. Seigle

TUNGSTEN incandescent lamp filaments possess a typical structure of elongated crystals generated upon heating the silica-alumina doped wire rapidly to 2200°C or above.&apos; It is known that these very long grains exhibit a preferred orientation, but there is disagreement in the literature about the direction. Rosi,2 and later Rieck; reported that the <135> direction of the large grains in doped wire tends to be parallel to the wire axis, but other investigators have reported that <110> is the preferred direction. Some further investigation of the orientations of large grains in tungsten wire is reported in the following. In the first series of experiments, 6-in. lengths of wire were heated rapidly in a bell jar. Current was passed through the wires and within 15 sec the wires had reached the grain coarsening temperature. 2 min was the annealing time. Wires were heated in hydrogen, nitrogen, and vacuum. Later, wires were heated in an evacuated tube furnace in which the tube was brought from 1000°C to the operating temperature within 25 sec and held 5 min at temperature. Temperatures were measured with an optical pyrometer. After heating, the wires were electro polished and etched, and the orientations of the large grains determined by the Laue back-reflection technique. Most of the experiments were carried out on a single spool of 5-mil silica-alumina doped wire, but a few tests were made with 5-mil thoriated tungsten wire and 10-mil undoped wire. 5-mil silica-alumina doped wires were reduced to smaller diameters by electropolishing for one series of experiments. Orientations of the large grains in silica-alumina doped wire heated in various atmospheres are presented in Figs. 1 and 2 as plots of the direction of the wire axis relative to the cube axes of the crystals. For most of the conditions studied, the preferred orientation cannot be described as a single direction, but the points might be said to group themselves about the arc passing through <110> and <113>. This arc is the trace of the (211) planes and contains the <135> and <124 as well as <011> directions previously observed by other investigators. The preferred orientation of large crystals in silica-alumina doped tungsten wire might be most generally described, therefore, by stating that a (211 ) tends to be parallel to the wire axis. This is true also for wires reduced in diameter by etching and furnace heated, Fig. 2, i.e., the recrystallization texture is apparently unchanged upon removal of the outer layers and substantially independent of the temperature gradient within the wire.

Jan 1, 1962

By W. A. Ver Wiebe

The year 1939 in Kansas, with a production of 57,944,300 bbl. from 19,669 wells, shows a slight recession from the peak of oil production reached the previous year, when slightly over 59,000,000 bbl. of oil was marketed. The previous peak had been reached in 1917 with 45,451,000 bbl. marketed. Another still earlier peak had been reached in 1904, when slightly less than 5,000,000 bbl. was produced and sold. The production of gas probably reached a new peak during 1939 with a total of over 69 billion cubic feet. Between the peak of the year 1908, when over 80 billion cu. ft. was produced, and that of 1939 the production dropped to 16 billion cu. ft., in the year 1921. During the year 1458 wells were drilled. This figure is somewhat lower than that given in several trade journals, because it does not include wells that were deepened or recompleted in a different geological horizon. Nearly 75 per cent (1029) of the total number of wells were completed as commercial oil wells (824 in western and 205 in eastern Kansas). The commercial gas wells completed number 71, of which 24 are in eastern Kansas and 47 in western Kansas. The remaining completions include 154 dry holes in eastern and 204 dry holes in western Kansas. Based on daily potential capacity the new discoveries of the year accounted for a cumulative initial production of 264,000 bbl. in eastern and 1,158,827 bbl. in western Kansas. It is interesting in this connection to note that the number of wells completed in the state rose gradually to a first peak in 1904, when 2782 were drilled. The number dropped off rapidly to 368 three years later, but rose to the second and highest peak in 1918, when 4671 wells were completed. In the period between 1904 and 1912 more gas wells than oil wells were completed. Between the high peak of 1918 and the somewhat lower peak of 1937, the low point was reached during 1931 with the completion of only 470 wells. In the matter of new pools discovered, Kansas again ranks high. The exact number depends somewhat upon the interpretation of a "new" area—whether it should be called a new pool or a long extension of an older pool. In some places this determination cannot be made until more wells are drilled within the area. Therefore, the figures given

Jan 1, 1940

By C. E. Nighman, R. S. Foster

The following is a description of the methods used in rescuing men and extinguishing the underground fire at the Pennsylvania mine, Butte, Mont. , This fire, which cost the lives of 21 men, began about 9 p.m., Feb. 14, 1916, at or near a ventilating fan on the 1,200 air-shaft station. This shaft at that time was downcast, while the main hoisting shaft was upcast. Owing to the proximity of the fire to the air shaft, the air in the latter soon became heated, and as the fan on the level was not running— the power having been cut off shortly after the outbreak of the fire—the air shaft became upcast to the 300 level. At this point a blanket of cold air from the surface caused the smoke and gases to be drawn in on that level and carried down again through the workings to the 1,200. A short time after the discovery of the fire, water was turned down the air shaft through a series of pipes around the collar of the shaft, which caused the smoke to recede below the 300, so that within 2 hr. it was possible to search that level for the missing men. From the above it will be apparent why the air shaft was upcast instead of downcast, as under normal conditions, and why men were suffocated at considerable distances from the seat of the fire. The smoke and gases that came up the main hoisting shaft did not diffuse through the workings to any extent. There are doors on all levels in the connections to the main hoisting and air shafts, but in the confusion and running around many of these doors were left open, and this undoubtedly caused the smoke and gases to spread more rapidly than they would otherwise have done. It was necessary for most of the men on the various levels to pass close to the air shaft in going to the hoisting shaft, and when they encountered the smoke and gases in that vicinity a number turned back and climbed down with the direction of the air currents and were then suffocated, while all those who passed through the pall of smoke to the main shaft were saved. There were 220 men in the mine that night, and all but 25 were hoisted to the surface within 30 min. after the discovery of the fire. Of the 25, five went out through the Tramway mine, and one through the Moun-

Jan 1, 1918

By H. M. Davis, T. S. Jones

A methodfor accelerating the reduction of a metal oxide by carbon monoxide is to incorporate in the reduction system a nonreducible oxide which has a strong affinity for carbon dioxide and will remove it from the product gases. The effectiveness of this method was investigated by veduction experiments on specially prepared powder mixtures of SrO-ZnO ("active&apos;.) and SrCO3-ZnO (reference). Measurements at 750o and 677°C showed that the rate of reduction of ZnO by CO was as much as an order of magnitude greater in the presence of SrO. Under the experimental conditions at least as much CO2 as generated by veduction was absorbed when SrO was present. Enlzancernent of the veduction rate by SvO resulted from modification of&apos; gaseous djfitsion processes. THE specific question posed in this investigation was whether the reduction reaction CO + ZnO - Zn(g) + COa [1] could be accelerated by incorporating strontium oxide into the oxide charge undergoing reduction. Provided the strontium oxide was active enough, it could remove carbon dioxide from the product gases of ( 11 and form strontium carbonate, thus modifying Reaction [ 1] to CO + ZnO + SrO = Zn(g) + SrCO3 [ 2] This study of the comparative rates of Reactions [ I] and [2] can be considered as a particular case of a general scheme for increasing the rates of reduction of metal oxides by carbon monoxide. The limits of applicability of this scheme are indicated in the simple thermodynamic analysis presented in the appendix. This analysis primarily dictated the choice of the system, CO-ZnO-SrO, employed in this investigation. In addition, it was thought that a study of this scheme by use of the CO-ZnO-SrO reaction system would be of special interest in view of indications in the literature1-3 that the gaseous reduction of zinc oxide is prone to rate control by diffusion in the gas phase. The distinction should be pointed out between this and other efforts to increase the rates of reduction reactions through the use of addition agents. Additions of a wide range of chemicals have been tried with de- grees of apparent success varying from slightly negative to highly positive. The reasons for making additions have included the use of salts to produce effects akin to catalysis,4, 5 the alteration of the microstruc-tural details of the reduction process (including solid-state diffusion),6-8 and the conversion of an en-dothermic reaction into one that is exothermic or autogenous.9-12 The means used to attempt alteration of the enthalpy change has commonly been to incorporate lime into the charge, so that heat is generated by reaction with either of the reaction products, carbon dioxide or water. The use of lime in this way makes endeavors such as that of Edstrom and Wiberg similar to the present one. Furthermore, the basic principle behind the present work has previously been set forth.13 However, a detailed investigation of the type of reaction described in this work does not appear to have been conducted. EXPERIMENTAL PROCEDURE From both conceptual and physical standpoints, Reaction [2] is to be considered as the sum of two reactions:

Jan 1, 1968