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By John R. Anderson, Michael B. Bever

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By J. A. M. van Liempt

Since the discovery of von Laue, that a crystal forms a natural grating for X-rays, our knowledge of the structure of solids has gone forward with rapid strides. This progress is not only of purely scientific interest, but has also yielded direct technological results. One of the most valuable results is the broadening of our knowledge of the structure of pure metals and alloys. To promote these studies it is often desirable to have at our disposal pieces of metal consisting of one single crystal. As is so often the case in the natural sciences, we obtain the best results by making our earliest experiments on pure, simple materials and avoiding unnecessary complications. The Cryogen Laboratory at Leyden followed this method with much success, because the work was done at such low temperatures that the heat movement of the atoms was almost absent. Similarly we can simplify the studies of metals by leaving out of consideration the influence of the grain boundaries and the mutual influence of the crystals by using unicrystalline instead of polycrystal-line metal. Methods of making single crystals have been scientifically studied during the past few years. Some methods were already known in the arts, but these have been improved and new methods have been developed. The methods for making metallic single crystals may be divided into the following groups: A. From the liquid state B. From the gaseous state C. Electrolytically D. By recrystallization in the solid state Method A 1. Tamwmnn's Method1—Tammann succeeded in making bismuth single crystals of a maximum length of 20 cm. by undercooling the molten metal 0.1 to 0.3' G. below its melting point in glass tubes of a maximum

By V. N. Antaki

ELEMENTAL phosphorus (referred to as P,) is a true mineral product that has developed, in the relatively brief span of a century, from a laboratory curiosity to a heavy chemical. Annual production now exceeds 300,000 short tons. Continued rise in production has been predicted, consistent with new applications for P, derivatives and the expected population increase. In itself elemental P, is valuable chiefly as an 'intermediate chemical. The principal end uses at present are in inorganic phosphates, both simple and complex, of sodium and potassium, used in water treatment and detergent compounds, leavening agents, food supplements, and dentifrices. Organic P, compounds are important as plasticizers, oil additives, flotation agents, and more recently as gasoline additives (TCP being the outstanding example). The increasing use of high-analysis water-soluble and liquid solution fertilizers, as well as the direct application of phosphoric acid to the soil, will probably be the most significant factors in P, production growth rate. Coke oven plants now using sulfuric acid to fix byproduct ammonia values will gradually switch to phosphoric acid in order to market a fertilizer with completely available values. Recently sponsored experiments show that phosphoric acid can be directly admixed with cattle and poultry feed to produce rapid growth. Both P, compounds and modifiers for oil well drilling mud show increasingly promising significance.

Jan 3, 1957

By W. I. Duvall, D. E. Stephenson

A theoretical solution is given for the energy that is radiated outward when either a cylindrical or spherical cavity located underground in a uniform stress field is suddenly created or enlarged. The method of derivation shows that the stress field in the solid rock surrounding the opening does work on the rock because of elastic displacements that result when the size of the cavity is increased. The amount of this work is sufficient to account for both the increase in the strain energy in the rock surrounding the opening and the seismic energy that radiates outward. Thus, the source of the radiant seismic energy is mainly the gravitational potential energy and not the strain energy stored in the rock. The amount of the radiant seismic energy is directly proportional to the volume of the rock removed from the opening or relieved of stress. Seismic energies from rockbursts are compared with earthquake energies. Also, the amount of gravitational potential energy released by underground explosions is calculated and found to be small compared to the seismic energy generated by the detonation of the explosive. A review of the early literature on rockbursts shows that a number of investigators calculated the amount of energy released by rockbursts. 1-5 However, none of these papers give the formula used to make these calculations or a reference to the derivation of any formulas. The general impression that one obtains from these early papers is that the main source of the seismic energy released by rock-burst is the strain energy stored in the rock before it is fractured. However, a few of the early papers appear to have considered the solid rock at a distance from the mine opening as a possible source of the seismic energy. Recently Black and starfield7 gave a theoretical solution for the strain energy in a stressed plate with and without a circular hole. Also, Press and Archambeau8 gave the theoretical solution for the seismic energy released when a spherical cavity is created in rock subjected to a three-dimensional stress field. Both of the above theoretical papers start with the condition of no opening and calculate the strain energy before and after the opening is suddenly formed. Neither of these papers appear to have calculated the work done by the applied stress field as the cavity is enlarged. The rockburst problem associated with deep mining is concerned with the failure of the solid rock surrounding an underground opening. Therefore, it seems appropriate to consider theoretically the problem of suddenly enlarging the size of an existing opening. The purpose of this paper is to present the theoretical solution for the energy that is available for release as seismic energy when an underground circular tunnel or spherical cavity is suddenly enlarged in diameter. To keep the mathematics as simple as possible, a uniform radial applied stress field is assumed and the rock is assumed to be isotropic, homogeneous and perfectly elastic.

Jan 1, 1965

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 M. H. Richman, E. S. Meieran

An analytical method is presented which enables the electron diffraction patterns from a twinned region to be indexed. The method has only been applied to (112) twins in bcc lattices, but can easily be adapted to other types of twinned lattices. Calculations of all twin spots, including those superimposed on matrix spots, is made possible by this method. SINCE the advent of transmission electron microscopy, the analysis of selected-area electron diffraction patterns has become very important in the interpretation of electron micrographs. Frequently, as in the case of some martensites, twinned areas are observed and give rise to complex diffraction patterns, which so far can be analyzed only for the simplest orientations of the thin foil specimen with respect to the electron beam. In order to simplify the analysis of twin patterns of more complex orientations, an analytical method was devised which is capable of predicting the positions of all reflections from both matrix and twin regions for all possible foil orientations. Although the method has only been applied to the case of bcc metals twinned about a (112) plane, it is equally applicable to other Bravais lattices. This method has been successfully applied to selected-area electron diffraction patterns of Fe-Ni and Fe-Ni-C martensites and drawn tungsten wire. PROCEDURE Imagine the reciprocal lattice corresponding to a bcc material, with each point hkl representing the crystallographic plane (hkl). Since the extinction conditions require that for this lattice, only reflections where h + k + 1 = even integer are allowed, the three dimensional reciprocal lattice is actually fcc. Since in real space twinned regions and matrix regions are mirrored across a (112) plane, the twinned reciprocal lattice is derived from the matrix reciprocal lattice by a rotation of 180 deg about a (112) direction. While it is possible to calculate how a point hkl will shift under a twinning transformation to a new point htktlt using only the reciprocal lattice based on the orthonormal vectors [100], [010], and [001], the calculations are greatly simplified if a new orthonormal coordinate system containing the twin axis is introduced. The twinning operation then becomes a simple rotation of 180 deg about a principal coordinate axis (in this case the twinning axis), and a retransformation back to the original reciprocal space will give the position htktIt of the twinned reflection.

Jan 1, 1963

By A. G. Metcalfe, Koeneman

A study of the structure of chemically deposited nickel by Goldenstein, Rostoker, Scpssberger, and Gutzeit has been reported recently. In this work it was shown that the nickel deposit produced by the catalytic nickel-reduction process was an amorphous solid. Crystallization occurred at elevated temperatures when the original powder pattern which showed only a diffuse ring with a d-spacing of 2.01A became sharp, revealing nickel and nickel-phosphide lines. The phosphide was indexed provision%lly on a tetragonal lattice of parameters a = 9.01A and c = 4.42A, which is in reasonable agreement with the structure of Ni3P proposed by No-wotny and Henglein.3 The transformation from the amorphous to the solid state occurs abruptly (e.g., after 7 min holding at 400°C) with the evolution of considerably more than 1000 cal per gm-mole. A more detailed analysis of these effects requires a knowledge of the solubility of phosphorus in nickel. Konstanti-now3 mapped out the phase diagram in 1908 but did not determine the solid solubility. The eutectic was placed at 11 pct P and 880°C. The purity of typical catalytic nickel deposits is very high.' Spectrographic analysis for heavier elements showed only trace amounts of aluminum, calcium, iron, magnesium, lead, and silicon. The term "strace" is a qualitative definition for less than 0.1 pct and probably less than 0.01 pct. Analysis for the interstitial elements yielded 0.04 pct C, 0.0023 pct 0, 0.0005 pct N, and 0.0016 pct H. Some of this material with 7.5 pct P was used in the present work. EXPERIMENTAL METHODS Alloys were prepared from carbonyl-nickel shot and a master composition containing 7.5 pct P. Cold-crucible, nonconsumable-arc melting was used.

Jan 1, 1959

By D. K. Crampton, H. l. Burghoff, J. T. Stacy

The study of copper alloys of the age-hardening type has received considerable attention, and, among the alloys which the authors have, considered, those containing small amounts of nickel and phosphorus as essential constituents seem especially interesting. Such alloys have attractively great capacity for being hardened and also have relatively high electrical and thermal conductivity in the hardened state. In addition, it has been found that the increase in hardness and strength imparted by aging can be greatly augmented by cold-working, so that excellent combinations of conductivity and strength are obtainnble. In view of the possible importance of the alloys, it was considered desirable to investigate the solubility relationships in the copper-rich portion of the copper-nickel-phosphorus system. This paper present's some of the results obtained in this investigation to date and also gives propertics of typical alloys that appear to be of commercial interest,. Review of literature Copper-nickel System,.—The binary coppcr-nickcl system has long been known to consist of a series of simple solicl solutions, copper and nickel being miscible at all tempcrat'ures and concentrations. This was establisl~cd by Guertler arid Tammannl in 1907 and confirmed by Tafel2 in 1908. Copper-phosphorus System.—The copper phosporus system has been studied by numerous investigators, so that the copper-rich portion is now definitely known. As most recently determined by Lindlief," his system has a cutectic at 8.38 per ccnt P, cuteetic temperature being 714° C. Components of the cutectic are Cu3P and alpha solid solution. Solid solubility of phosphorus in copper, according to Mertz arid Mathewson decreases from a maximum of about 1.75 per cent at 714' C. to about 0.6 per cent at 300' C.

Jan 1, 1940

By D. K. Crampton, H. l. Burghoff, J. T. Stacy

The study of copper alloys of the age-hardening type has received considerable attention, and, among the alloys which the authors have, considered, those containing small amounts of nickel and phosphorus as essential constituents seem especially interesting. Such alloys have attractively great capacity for being hardened and also have relatively high electrical and thermal conductivity in the hardened state. In addition, it has been found that the increase in hardness and strength imparted by aging can be greatly augmented by cold-working, so that excellent combinations of conductivity and strength are obtainnble. In view of the possible importance of the alloys, it was considered desirable to investigate the solubility relationships in the copper-rich portion of the copper-nickel-phosphorus system. This paper present's some of the results obtained in this investigation to date and also gives propertics of typical alloys that appear to be of commercial interest,. Review of literature Copper-nickel System,.—The binary coppcr-nickcl system has long been known to consist of a series of simple solicl solutions, copper and nickel being miscible at all tempcrat'ures and concentrations. This was establisl~cd by Guertler arid Tammannl in 1907 and confirmed by Tafel2 in 1908. Copper-phosphorus System.—The copper phosporus system has been studied by numerous investigators, so that the copper-rich portion is now definitely known. As most recently determined by Lindlief," his system has a cutectic at 8.38 per ccnt P, cuteetic temperature being 714° C. Components of the cutectic are Cu3P and alpha solid solution. Solid solubility of phosphorus in copper, according to Mertz arid Mathewson decreases from a maximum of about 1.75 per cent at 714' C. to about 0.6 per cent at 300' C.

Jan 1, 1940

By W. R. Crane

Mining of the red iron ores of the Birmingham district has been carried on energetically during the past 60 years, and their development has created a large iron and steel manufacturing center, the only important one in the South. The district produces approximately 10 per cent. of all the iron ore of the United States (80 per cent. of the Alabama ore mined is red ore); also, 40 of the 400 blast furnaces of the country are in the district tributary to Birmingham. The rapid growth of the district has been made possible through investigations that resulted in radical changes in furnace practice, and a still greater impetus will come from the study of the low-grade, high-silica ores, as a result on which they will be made amenable to treatment by concentration. Mining practice in this district has been comparatively simple because of the occurrence of the ore; but with the rapid extension of the workings and the disturbed condition of the ore bed at some distance from the outcrop, more difficult conditions are encountered and the tendency is toward worse rather than better conditions. Should the high-silica ores of the lower bench of the Big Seam become available through beneficiation, mining practice will have to be modified to meet the new conditions, which will be rendered more difficult by the increased weight of cover that will exist at considerable distances from the outcrop. Support of workings will require greater attention and the efficient and economical operation of the mines will depend largely on the successful solution of the problems of working and handling the ore. History and EaRly Development The first explorers of the coal and mineral lands of Alabama were blacksmiths and mechanics mustered out of the army after the war of 1812. These men recognized the red rock of the Birmingham district as iron ore, and utilized it in making cooking utensils and farm implements. The first blast furnace was built and operated at Russellville in 1818, where also was a foundry and rolling mill. Soft ore was used at that time, but, in 1864, the first red hematite ore of Red Mountain was smelted, near Irondale. Birmingham was founded in 1871, and the successful use of coke in making pig iron in 1876 was the beginning of

Jan 1, 1925

By A. Satter, J. M. Campbell

Reported herein are the results of a careful and detailed study of the non-ideal behavior of pure gases and their mixtures. Included are: (1) new data on five ternary systems composed of methane, ethane and H2 S; (2) a simple compressibility factor correlation that is inherently superior to present correlations, particularly for gases containing H2S and CO2; and(3) a detailed study of combination rules and the effect of system composition on the choice thereof. This study makes use of the rather large mass of data already available in the literature. A complete re-examination of the data and ideas presented in the last 25 years was considered desirable as a prelude to our basic concern — the effect of diluents on gas behavior. A consideration of both the macroscopic and microscopic properties of gases provides a better insight which, in turn, gives a firmer basis for improved correlation techniques. Such a study has shown that expressing the compressibility factor Z as a function of acentric factor w, as well as reduced temperature and pressure, yields a correlation that is broader in scope. The study of various combination rules has shown that better results are obtained by "tailoring" the rule used to the system composition. To do so improves the basic reality of results by overcoming some of the anomalies often found when using Kay's rule alone. Tentative recommendations are made regarding the most reliable combination rule for use with a given class of gas. The data presented are useful for estimating the direction and magnitude of the expected deviation when using a given rule. Although more work is needed, particularly around the critical region and with CO2 mixtures, the advantage of the classification scheme proposed is apparent. INTRODUCTION When one attempts to write a PVT equation to fit the data for actual gases, greater precision is obtained by the use of a multiple number of empirical constants. This has lead to multiple-constant equations such as Benedict-Webb-Rubin, Beattie-Bridgman, Keyes, etc., which are capable of yielding very precise results for pure gases in a range for which data to get the constants are available. As a matter of practicality, though, the use of such equations for gas mixtures is limited. Because of the infinite number of gas analyses available, any attempt to compile the constants needed requires a prohibitive amount of experimental data. This could be overcome by the use of a combination rule, but there is no real advantage in doing so because the end result offers no practical impovement over the Z factor correlation. The most widely used method of predicting the volumetric properties of pure gases is based upon the "theorem of corresponding states". According to this theorem, "all pure substances have corresponding molal volume at corresponding temperature and pressure if the reference point of correspondence is the critical point". Generalized compressibility charts for gases were prepared first by Cope and associates1 in 1931 and later by Brown and co-workers2 in 1932. However, the most commonly used charts are those of Dodge,3 Nelson and Obert,4 Hougen and atsson: and Standing and Katz.6 The work of Katz and co-workers has provided us with basic data for the hydrocarbons most widely used today. Their original chart6 was compared with a relatively large amount of multi-component data for gases consisting almost entirely of normal paraffin hydrocarbons. A deviation of only + 1.2 per cent was obtained.39 In the 20 years following publication of this work it has been found that the behavior of most mixtures of paraffin hydrocarbons could be predicted by this correlation within at least 5 per cent. Where difficulty has been encountered it has largely involved one or more of the following circumstances: pressures above 4,000 psig, mixtures containing large amounts of heavy ends and/or aromatics, systems in the critical region and mixtures containing polar compounds and/or CO2. The abnormal error sometimes found with such gases, not too unexpected for this method, is

By R. Maddin, S. K. Tung

SUCCESS of the dislocation theory in formulating the transitional lattice theory proposed by Har-greaves and Hill in 1929' is well established for low angle grain boundaries. The theoretical work of Burgersa and Read and Shockley,3 together with the experimental observations of Aust and Chalmers4 and Parker and colleagues,6 leaves little doubt as to the structure of grain boundaries with differences of orientations up to between 15" and 20". Beyond these angles, the structure of the boundary is not so clear, and is still a matter for conjecture. There have been notable experiments devised from which the data could be used to calculate energetics for possible arrangements of atoms in forming a large angle boundary.6 Most of these experiments deal with diffusion through and along the grain boundary. The recent work of Rhines and Cochart7 and Rhines, Bond, and Kissel18 was concerned with the relative movement of grains in aluminum bicrystals under constant tensile loads with their boundaries aligned at 45 " to the tension axis. The gliding along the grain boundary was cyclic and began after an incubation period. The velocity of gliding increased with the sum of the angular difference, 8, between the operative slip direction in the conjugate crystals and the angular difference between the active slip planes as measured between their traces upon the grain boundary. The initial gliding rate varied with temperature, and the logarithm of the average gliding taken over a considerable period was a linear function of the reciprocal of the absolute temperature: the slope gave an activation energy of 11,000 ±1,000 cal per mole. Since the rate of grain boundary shear is sensitive to the misorientation of the grains themselves, as shown by several workers,7,8 it is suggested that further work of this type might be fruitful in adding information regarding the behavior of boundaries under stress. The techniques devised by Chalmers" added impetus to the facility for observing grain boundary behavior, in that they provided a simple means for producing bicrystals of predetermined orientation so that the angle of the boundary could be controlled,

Jan 1, 1958

By A. U. Seybolt

The solubility of oxygen in a iron has been determined in the range between 700° and 900°C. The solubility is a function of temperature and varies from about 0.008 pct oxygen at 700°C to atureandabout 0.03 pct at 900°C. The heat of solution is approximately +15,500 cal per mol. AS pointed out in a recent paper by Kitchener et al.,1 there has been a lack of agreement among many investigators even as to the order of magnitude of the solid solubility of oxygen in the various forms of iron. This lack of agreement is attributable in large part to the difficulties in the determination of a small oxygen solubility; but because the problem has remained so long unsettled, it also indicates a lack of interest which is rather surprising when the demonstrated importance of small amounts of soluble nonmetallic impurities in iron is considered. The work of Kitchener et al. apparently leaves the solubility of oxygen in iron in a satisfactory state, but no attempt was made to investigate the solubility in a iron. The solubility of oxygen in a iron is actually of greater interest, since it is in this form that iron and mild steels are employed ordinarily. That the effect of oxygen in iron is of more than theoretical interest has been well established by Fast,' and more recently by Rees and Hopkins," who demonstrated that oxygen in the range between 0.0008 and 0.27 wt pct has a pronounced effect upon the mechanical properties. Previous Work and Methods Used To report in detail the literature relating to the solubility of oxygen in a iron would require an inordinate amount of space. For those interested in reviewing this work, a bibliography4-13 of the more significant papers is appended. In general, two methods of studying this problem have been used. One is the gas-metal equilibrium method where the H2O-H2-Fe or the CO2-CO-Fe equilibria have been used. The other is the more direct approach of the oxidation of thin strips of pure iron by packing in mill scale or by air or gaseous oxygen at some desired temperature. In this method oxygen is allowed to oxidize the surface and then to diffuse inward until saturation is obtained. In the gas-metal equilibrium method the oxygen dissolved in solid iron at a given temperature is proportional to the ratio of the water vapor-hydrogen pressures or the CO2-CO pressures over the sample for small ratio values. If the ratio becomes higher than a critical value, then an oxide phase makes its appearance (the solution becomes supersaturated). In principle, it is possible to use a series of H2O/H2 or CO2/CO ratios and to find by analysis the corresponding amounts of oxygen in solid solution at constant temperature. At the point where a very small increase in the gas ratio (increase in oxidizing powder) produces a large increase in oxygen content, the solid solubility limit is reached. Alternately, if the critical ratio is known, it is possible to use the procedure of Kitchener et al.1 and to use a ratio which is near but below the critical one. The solubility corresponding to this lower ratio will not be the saturation solubility at the temperature employed, but the saturation solubility can be calculated by multiplying the measured solubility by the critical ratio over the ratio used. However, in the case where oxygen gas is the oxidizing medium, the saturation solubility is not a function of pressure, providing the pressure exceeds the dissociation pressure of FeO in equilibrium with iron. This is 1.2x10-16 mm at 800 °C, according to Dushman." As pointed out by Darken17 in discussing the FeO phase diagram, most of the possible errors tend to yield high values of oxygen solubility. For example, one circumstance which evidently caused the reporting of many high values was the use of finely divided or powdered iron in the gas equilibrium method. Because of the large surface area of such a sample, and the likelihood of some surface contamination if only by exposure to air, the results tended to be high. The direct oxidation method which was used in this work has the advantage in that it is simple and direct, but it suffers from one disadvantage: equilibrium can only be approached from the low oxygen side. The important factors to be kept under control are the following: 1—use of high purity iron to avoid internal oxidation (oxidation of readily

Jan 1, 1955

By Sherwin F. Kelly, Bela Low, William B. Creagmile

Electrical methods and instruments for geophysical exploration have been almost exclusively applied, during these years of development of the art, by a few companies specializing in this field. The control of patents, the cost of the instruments and the general lack of published information on details of field procedure and office interpretation have given these owners a monopoly in carrying out electrical surveys. The development of the Megger Ground Tester1 seems likely to change this situation, and to enable mining engineers and geologists, without special training in geophysics, to carry out simple reconnaissance electrical surveys. Nevertheless, the need for such special training and experience in planning surveys and interpreting their results remains, and probably i always will remain, indispensable for a successful outcome. The unique thing about, the Megger Ground Tester, which gives rise to this hope for its general use, is its simplicity of operation. The four binding posts of the instrument are connected by insulated wires to four stakes driven into the ground at appropriate points. The crank of the Megger is then turned, and the resistance of the ground between the two inside stakes is read directly, in ohms, by the deflection of a pointer over a scale. The apparatus is shown in Fig. 1. Fundamentally, the principle of operation is that of determining the resistance of a four-terminal conductor, as applied by Frank Wenner to the measurement of earth resistivity. "A four-terminal conductor is a conductor provided with two terminals to which current leads may be connected and two terminals to which potential leads may be connected. The resistance of such a conductor is the difference in potential between the potential terminals divided by the current entering and leaving

Jan 1, 1932

By V. F. Swanson

At the AIME meeting in Tampa in Oct. 1966, an empirically developed equation was presented which allowed the calculation of free settling velocity for any sized particle: 1 [ ] This equation requires the use of two parameters a and p which are coefficients derived from boundary layer theory.2 It was possible to develop values of a and p for several minerals by back calculation of published data. The original equation had one major flaw. When the fluid density exceeds the density of the solids, the solution to the equation becomes imaginary. A flaw was indicated also by the fact that galena and sylvite both having cubic cleavage, did not have similar values for a and b. Galena gave calculated values of a = 1.082 and g = 3.11, while sylvite gave values of a = 1.870 and p = 2.56. These flaws prompted further study of the equation, resulting in the following empirical modification: [ ] It is obvious a real solution of the equation is possible for all values of ps and p. When PL > PS, V is negative, indicating that the particles will rise against the attraction of gravity. The validity of the modification is borne out by the fact that when values of a and p were back calculated for galena and sylvite using the modified equation, both minerals gave values of a = 1.038 and p = 3.01. With the modification shown in Eq. 2, Newton's friction factor becomes [ ]

Jan 1, 1976

By M. A. Childers

Recent work with controlled laboratory tests.' field experience and a new analytical approach indicate that casing centralization, pipe movement and relative rheological properties between the mud and cement (yield point and density) are the three controlling factors in successfu1 primary cementing of dual casing. Turbulent flow has been demonstrated to be unnecessary under the severe displace ment conditions of parallel dual strings of casing. Simultaneous reciprocation of dual casing in directionally drilled boreholes is highly dependent on centralization and on the rapid initiation of pipe movement once the casing has been run to total depth. Successful cementing of 30 out of 32 dual, 3%-in casing wells substantiated these conclusions. A review of 15 dual, 3 1/2-in. casing wells completed prior to the adoption of these principles disclosed only one success. Mathematical and graphical techniques permit the engineer to analyze and anticipate the success or failure of a cementing operation. Standoff, mud displacement and reciprocation can be analyzed mathematically and planned in deep, directional or straight boreholes by review of annular geometry, relative rheological properties between the mud and cement, and forces caused by caring weight, functional drag and differential sticking. Introduction The objective in primary cementing is to displace the drilling fluid with cement that will bond to the formation and casing to prevent communication through the annulus. The predominant cause of failure appears to be channels of gelled mud that remain in the annulus after cementing.1 '* Past investigations have noted many procedures that could improve the displacement process.2-' These procedures include centralization, chemical preflushes, mechanical mud cake removers, controlled flow rates in certain regimes, pipe movement an1 control of mud and cement properties. Not until recently have the effects of many of these procedures been isolated so that their individual importance could be determined. In a recent paper,' a comprehensive and analytical laboratory study of various factors controlling the displacement process concluded that there are three major factors in obtaining complete mud displacement by the cement slurry. 1. Good relative rheological properties between the mud and cement. The cement should be heavier and have a yield point and plastic viscosity higher than the mud being displaced. Buoyancy forces often can dominate the displacement process. 2. High degree of standoff or centralization. The more centered the casing, the greater the likelihood of complete mud displacement and removal. 3. Pipe movement obtained by rotation or reciprocation. Often unfavorable rheological properties between the mud and cement, and poor standoff can be compensated by pipe movement. This work demonstrates the compatibility of the latter concepts with field results extended to the more severe dual casing displacement process. Early Experience With Dual 3'/t-In. Primary Cementing Early slim casing completions in the West Delta Block 73 field, offshore Louisiana, included 17 dual 3%-in., 3 single 3% -in. and 1 dual 2% -in. casing installations. Table I provides data on these earlier wells. Usually, common Class A cement was placed across the pay zone and 12 percent gel cement was placed to a height of 500 ft above the highest productive sand. Centralizers (6%-in. OD maximum expansion) were placed two or three per joint on both casing strings from total depth through the completion intervals and at least one per joint for the remainder of the cement sheath. A number of techniques and procedures were attempted to improve cementing success. Casing was run simultaneously or separately with a number of mud conditioning and circulating techniques. Mechanical aids such as cement bonders, slmiding sleeves, turbulizers and various sizes and strengths of centralizers were used. Common and gel cements were mixed with fresh or sea water with a number of different additives to control retardation and dispersion. Cements were thinned and mixed at high rates to try to induce turbulent flow in the annulus. On one well the "slow flow" method was used." Perforating was accomplished with a jet orienting gun. Unsuccessful cement jobs were indicated by production of extraneous fluids or by pressure communication between zones. On test, five wells flowed water, four flowed sand and six had pressure communication with the other string or the 10%-in. casing. A total of 25 remedial squeeze ce-

Jan 1, 1969

By Herbert Banks Johnson

DURING the past 10 or 12 years very little information has been made generally available concerning the commercial possibilities of separating materials by means of static electricity; and yet during that same period important improvements have been made in various branches of the science of electricity, which, when taken together, and applied to electrostatic separation, have resulted in important improvements in that art as well. For example, much improvement has been made in high-voltage electrical equipment such as full-wave vacuum-tube rectification and improved mechanical rectification. Great strides have likewise been made in the development of insulators for high-voltage work, not only in the materials used but also in the design of the insulators themselves. Again, in another field, the development of air-conditioning equipment has improved the technique of controlling the surface condition, through drying or humidifying, of the various materials that are passed through the electrostatic separator. In many authoritative publications and textbooks, the electrostatic separation process is declared to require a balance far too sensitive for general commercial application. For example, one publication1 in the past has referred to an unfavorable effect on the process caused by varying atmospheric conditions such as humidity. Some2 have even gone so far as to state that sunlight and shadows may seriously affect the separating efficiency of the process. Such statements may have been true in the early development of the art, when the source of static electricity was derived from a friction disk machine, such as the Wimshurst. The Blake Mosher equipment and the work of Huff in applying motor- generator sets, transformers and mechanical rectification overcame much of this kind of objection to the commercial application of the electrostatic separating process. Another objection made periodically is that it is generally considered necessary to feed the particles into the electrostatic field in a stream that

Jan 1, 1938

By O. N. Cole, R. E. Davis, T. D. Brotherton

Pvfoperties of rubidium and cesium are compared with those of other alkali metals. Methods for the preparation of rubidium and cesium metal are reviewed briefly, ad hazards and safety precautions required in handling rubidium and cesium metal are described. SimPle methods for handling laboratory quantities of elemental rubidium ad cesium under oil and under argon are illustrated. CESIUM and rubidium were both discovered by Bunsen and Kirchoff in the years 1860 and 1861. Cesium was discovered while Bunsen and Kirchoff were making a spectrographic study of spring water from Durkheim, Germany. It was the first element discovered by this technique. The element was given the Latin name "caesius" for sky blue because of the color it imparted to flames. Elemental cesium was first prepared by Setterberg in 1881 through electrolysis of a molten mixture of cesium and barium cyanides.' In 1861, Bunsen and Mirchoff discovered rubidium while making a spectrographic study of the alkali content of lepidolite ore from Saxony. Two prominent dark red lines appeared in the spectrum and so the element was named "rubidius" or dark red. In 1861 Bunsen and Kirchoff first prepared elemental rubidium through the electrolysis of molten rubidium chl~ride.~ The alkali metals are very similar in their chemical and physical properties. They are the most active metals, and all exhibit a single oxidation state of one. They are so reactive that they are never found in nature in the elemental state. The reactivity of he metals increases with atomic number. Rubidiurn and cesium ignite spontaneously in air and react explosively with water. This extreme reactivity makes necessary special equipment and techniques for the safe preparation and use of the metals. The cation: of Group IA can be separated from the metallic cations of other groups with relative ease, but the separation of the individual alkali cations is much more difficult because of their close chemical similarity. This close chemical and physical similarity of alkali metals can be inferred from the atomic radii, oxidation numbers, and ioni-zation potentials shown in Table I. A difficult but the most practical physical method of separating the elemental alkali metals from one another is by distillation. Only lithium has a boiling point sufficiently far-removed from the boiling points of the other alkali metals to make this method of separation feasible without elaborate and expensive equipment. This method is not used, however, for lithium because it possesses sufficient chemical dissimilarity from the other alkalies for it to be separated relatively easily as lithium hydroxide monohydrate or as lithium carbonate. Francium, the last member of the group, has no known stable isotopes. The naturally occurring

Jan 1, 1962

By Rudolf K. Berkhard

Static soil investigations with more or less heavy loads and extensive borings do not always have efficient results; also, they are very expensive. The new geophysical method of dynamic tests described herein is simple and cheap and avoids several disadvantages of the routine investigation, thus forming a useful supplement to the older methods and even at times replacing various static tests. The fundamental principle of dynamic soil tests consists in the application of artificial vibration. The technique employed is essentially geophysical in nature and in some respects is akin to seismic studies. Artificial vibration may be excited by centrifugal forces resulting from eccentrically supported rotating masses. The reactions of soil and structures caused by these vibrations may be measured. Their dynamic constants, such as amplitudes, phase speeds, damping, reflection, and interference effects, can be investigated. This geophysical method has been used for several years with increasing success. The results of these tests, summarized at the end of the paper, indicate that this method opens a new field for the pkactical engineer in investigating soils (capacity and formation), foundations, dams and structures, and especially buildings that must withstand earthquakes. Methods Static Method.—The first and oldest tests to investigate the bearing capacity of the soil were carried out by static weights. The penetration of these weights, however, depends not only on the soil but also on the size and the form of their lower surface. The length of time the load acts is also important. To imitate actual field conditions, heavy weights and lengthy tests are required, both of which are expensive. Furthermore, the influence of static weights affects only the surface and does not penetrate into deeper strata, therefore substitutes and supplements for static tests have to include the time factor and consequently lead to dynamic investigations. Such dynamic investigations also affect

Jan 1, 1940