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By E. S. Tankins, G. R. Belton

A simple solution model, based upon the formation of molecular species, is developed for strongly electronegative dilute solutes in liquid binary-metallic solvents. Two approximations are considered for the relative concentrations of the species: the random and the quasi-chemical. Equations are presented for the partial molar free energy, enthalpy, and entropy of mixing of the solute. An experimental study has been made of equilibrium in the reaction H2 6) +0 (dissolved) = H2O(g))for the liquid Cu-Co alloys. The standard free energy of solution of oxygen is presented as a function of composition for the alloys at 1550°C and as a function of temperature for five of the alloys. The experimental results for these alloys and also for Cu-Ni alloys are shown to be in reasonable agreernent with the theory in the random approximation. A knowledge of the thermodynamic behavior of dilute solutes in liquid metals and alloys is of importance in understanding and designing refining and alloy-making processes. Accordingly, several attempts have been made to derive suitable solution models to forecast the effect of a third component on the activity coefficient of such a solute in a metal. Alcock and Richardson' reviewed the literature prior to 1958 and also showed that a regular solution model gave a reasonable description in the case of metallic solutes but failed to account for the behavior of the more electronegative solutes sulfur and oxygen. These same authors2 later modified their model by using the quasi-chemical approximation3 to calculate the average composition of the first coordination shell surrounding each solute atom. This modified model was shown to lead to a better qualitative description of the behavior of the electronegative solutes; however, quantitative agreement with experimental data for oxygen in alloys could only be achieved by assuming a very small coordination number. The authors concluded that the major source of error in the model was the assumption that pairwise interaction energies were independent of composition. Substitutional and interstitial random solution models by Wada and saito4 are essentially similar to the first model except that the required interchange energies were derived from the modified solubility parameter equation of Mott, instead of from experimental binary data. Most recently Hoch5 has presented a statistical model for interstitial solutions and has applied the model to the Fe-C-O system. However, as the various interaction energies needed in the model had to be derived from the ternary data, the model does not promise well as a means of forecasting ternary behavior. Each of the above models carries the assumption that the strongly electronegative solutes have the same configurational environment as metallic solutes; i.e., the solute can be treated as a substitutional or interstitial atom in a quasi-crystalline lattice and is surrounded by a normal coordination shell of solvent atoms. There are, however, a number of facts which suggest that this is unlikely. First, the heats of solution are large, being more typical of molecule formation rather than alloying. For example, the heats of solution of monatomic oxygen and sulfur in liquid iron are -90 kea16,8 and -74 kea1,7, 8 respectively. These are to be compared with maximum heats of solution of metallic solutes in liquid iron of about -13 keal (silicon is an exception with -28.5 kea17). The large depression of the surface tension of liquid iron by trace amounts of the electronegative solutes oxygen, sulfur, and selenium9 suggests, by analogy with aqueous systems, the possible existence of polar molecules in the liquid. The effect of these solutes is at least three orders of magnitude greater than normal metal solutes.10 As has been pointed out by Richardson,11 the electron affinities and ionization potentials of oxygen and sulfur are such that it is likely that they exist in metallic solution as negatively charged ions. If this is so, and it is assumed that electrostatic forces play an important role in determining the configuration, it is unlikely that the stable configuration will be that of an isolated ion surrounded by a symmetrical coordination shell of solvent ions. It is more likely that the energy of the system would be lowered by the formation of solute-solvent screened dipoles. The above arguments suggest the formation of "molecular species" between solute and solvent atoms. The idea of the existence of molecular species in such solutions is not new, however', for Marshall and chipman12 have explained in a semi-quantitative manner the C-O equilibrium in liquid iron by postulating the species CO. Chen and Chip-man13 interpreted their measurements on the Cr-O equilibrium in iron in terms of the species CrO. Zapffe and sims14 have also postulated the existence of such species in liquid-iron alloys.

Jan 1, 1965

By Dennis E. Peterson

Land subsidence had been observed in recent years throughout the Southwest. Particular examples of this phenomenon that have gained wide publicity axe in the Long Beach and Central Valley areas of California and, the Houston area of Texas. Less well known is the fact that the land surface Is subsiding in many parts of Arizona, including the Phoenix area. The causes of this problem vary from place to place, as do also the rates of subsidence. In Houston it has been related to pumping water from artesian aquifers; in Long Beach to the development of oil fields; and in the Central Valley to both the lowering of artesian pressures in deep aquifers and the wetting of poorly consolidated surficial deposits. The mechanism by which subsidence occurs in southern Arizona, even though it can be correlated with the continued lowering of ground water levels, is not as apparent as in these other cases. It is the purpose of this paper to examine both the causes and affects of land subsidence in southern and central Arizona.

Jan 1, 1965

By Donald R. Mason, Daniel F. O’Kane

DIFFERENTIAL thermal analysis measurements have been used to determine the ZnTe-In2Te3 pseudo-binary phase diagram. Since ZnTe and In2Te3 are both semiconductors, any intermediate compounds formed in this system should also be semiconductors according to the rules delineated by Mooser and pearson.1 The compound ZnIn2Te4 was first reported by Hahn et a1.2 and it has subsequently been prepared and characterized electrically by several workers. A brief summary of this work has been presented by Mason and O'Kane3 who also report that the compound appeared to melt peritec-tically. The Zn-Te phase diagram has been investigated by Kulwicki4 who found that ZnTe has a melting point of 1290° + 2°C. The In-Te diagram published in Hansen' contains significant errors, and has been redetermined by Grochowski et al.6 However, both sources agree that the melting point of In2Te3 is 667°C, with the latter authors reporting the previously observed solid-solid transformation occurring at about 550°C. Hahn ef al.2 reported lattice-parameter values for the ZnTe-In2Te3 system. The 67 mole pct ZnTe-33 mole pct In2Te3 composition was the only

Jan 1, 1965

By K. G. Davis, P. Fryzuk

The diffusivity of silver in liquid tin has been determined, using the capillavy-reservoir technique, over the temperature range 250° to 500°C. The new value, D = 2.5 x 10'* exp(-2480/ RT) sq cm per sec, differs from that obtained by other workers in an earlier investigation. The analysis of data from the capillary-reservoir technique is discussed. In a recent investigation of the solidification of dilute alloys, values for the diffusion constant of silver in liquid tin were required in the analysis of the formation of impurity substructures. AS a result, measurements were made of the diffusion constants in the temperature range 250° to 500°C (melting point of tin 232°C), for the alloy concentrations used in the solidification experiments and at higher concentrations, to verify previous determinations.I)2 The capillary-reservoir method was adopted, using experimental procedures similar to those followed by Ma and Swalin,1 with the main exception that radioactive silver was used in the present investigation to facilitate solute-concentration measurements. EXPERIMENTAL PROCEDURE a) 100 ppm Samples. Glass capillary tubes of 2 mm inside diameter and approximately 5 cm- long were sealed at one end, evacuated, and filled with tin of 99.999 pct purity. The region of shrinkage near the mouth was cut off, and the tubes were then placed in a graphite holder and immersed, with the open end up, in an unstirred bath of alloy containing 100 ppm Ag 110, where they remained for periods of up to 30 hr. On removal from the bath they were cooled by an air blower. The bath was kept under a small positive pressure of argon, and the temperature controlled to within +1°C. A 10-hr diffusion period was used in the majority of the tests, scatter on runs of less than 5 hr being rather large. The procedure outlined above was chosen in preference to putting alloy in the capillary and pure tin in the bath, in order to avoid segregation when the tubes filled with alloy were first solidified. To minimize segregation when the diffusion period was complete and the capillaries again solidified, the earlier samples were held in thin-walled silica tubes which could be cooled very rapidly. Later tests were made in precision-bore Pyrex tubes, to eliminate effects caused by variations in the capillary diameter. No consistent differences in diffusivity as measured in the two types of tube were detected. After removal from the glass tubing, the samples were sectioned into 2.5 mm lengths and counted for y activity, using a scintillation counter with fixed geometry. Samples were also drawn directly from the bath and counted, so that values for C/C,, the ratio of the weight of Ag 110 in the sample to that in the bath, could be obtained. b) 5000 ppm Alloy. To check for possible effects of concentration, the silver content of the bath was increased to 5000 ppm. Complete mixing was found to have taken place in the capillary after a 10-hr period at 300°C. It appears that the greater density of the alloy was sufficient for buoyancy forces to cause instability in the alloy-tin interface, leading to rapid convective mixing. For the 5000 ppm alloy, therefore, the bath was of pure tin and the capillary tube was filled with alloy. With this arrangement, values of D consistent with those for the 100 ppm alloy were obtained, Fig. 1. CALCULATIONS OF DIFFUSIVITY The terminology used applies to a capillary of pure tin immersed in a bath of alloy. 1) Error-Function Method. under the present experimental conditions, the rod of liquid tin into which silver is penetrating may be considered semi-infinite. Assuming the concentration at the mouth of the tube to remain constant at Co, the concentration C at distance x from the mouth of the tube at time / is given by3 Plots of the inverse error function of (1 -C/Co) vs .v gave straight lines passing through the origin with slope 1/2-, x being corrected for shrinkage both on solidification and while cooling to the melting point (total correction about 6 pct at 500°C). Values for log D obtained in this manner are shown in Fig. 1. A least-squares fit to the relation D = Do exp(-Q/RT)

Jan 1, 1965

By James F. Neill, O&apos

Brown iron ore resources in Barbour, Butler, Crenshaw, and Pike Counties were investigated in a drilling program and geological study by the Federal Bureau of Mines in cooperation with the Alabama Geological Survey and the University of Alabama. The aggregate footage drilled was 18,010 linear feet. When developed, reserves of 12,664,000 long tons of crude ore were indicated, containing from 26.9 to 29.0 percent iron and 0.2 to 1.6 percent manganese under a maximum overburden of 40 feet. Total inferred crude ore for the four counties was calculated to be 827,700,000 long tons. Beneficiation of samples by simulated log washing and use of a 118-inch screen yielded from 46.8 to 51.7 percent iron and 0.2 to 2.6 percent manganese. Screen-test studies indicated no appreciable interlocking between the iron and manganese minerals and the waste particles of materials retained on a 200-mesh screen. Clay was prominent in micron-size slimes. Silica was deleterious in the minus 20-mesh size. While an indicated 2,198,000 dry long tons of usable iron ore can be recovered, sink-and-float tests show that it may be possible for 4,654,000 dry long tons to be recovered by other than log washing. However, applicable commercial processes have not been demonstrated.

Jan 1, 1965

By S. Feuerstein, J. M. Galligan

SURFACE effects in the deformation of metal single crystals have been noted by a variety of workers.&apos; A large majority of these experiments have used surface roughening or a second chemical constituent at the surface. We performed the following experiment to see how the presence of a fine polycrystalline layer influenced the stress-strain behavior of single crystals of zinc. Spherical single crystals oriented for single slip were acid-machined into cylindrical dumbbell-shape shear specimens having a gage length of 3.2 mm and a cross section of 20 sq mm. The crystals were then deformed varying amounts at the surface of the gage section with emery paper. Following this treatment, the crystals were heated for approximately 8 hr at 200°C. This resulted in a polycrystalline surface layer, with an observed grain size of approximately 1/10 mm in diameter. Deformation of these crystals was undertaken at 78°K in pure shear, the shear direction <1120> lying in the basal plane. The deformation apparatus has been described elsewhere.2 The presence of a polycrystalline layer markedly raises the first observed plastic deformation, as can be seen from Fig. 1. This yield stress is then followed by a region of low work hardening comparable to that observed in shear tests on similar untreated zinc single crystals. However, the extent of easy glide is quite seriously curtailed, and is followed by a more rapid increase in work hardening, reminiscent of Stage II observed in the deformation of fcc crystals. The higher yield can probably be attributed to the difficulty of penetrating the grain boundaries by dis locations from sources interior to the boundaries. If we associate this yield stress with this breakthrough, then we might expect that more dislocations would be trapped in the crystal than is normally the case. If there is an increased density of trapped dislocations, this could lead to an increase in the amount of trapping with increasing strain, giving a larger strain hardening in the crystal. Although other explanations can be given, it is quite tempting to characterize the region of increased work hardening as a manifestation of Stage II-type deformation. This seems reasonable if the polycrystalline layer is quite efficient in holding up a large number of dislocations. In zinc crystals, since it is well-known that the slip distance can be as large as the specimen dimensions, one would only expect to entrap a large number of dislocation with very large crystals or by applying surface layers. If this interpretation of increased strain hardening is correct, it might present a method of studying Stage II in single crystals of zinc. This research was supported, in part, by the Office of Naval Research (1959). The encouragement and stimulation given by Professor E. R. Parker is gratefully acknowledged.

Jan 1, 1965

Greater use should be made of lineations in investigations of the engineering properties of rock masses and in structural studies guiding prospecting programmes.A prominent alignment of elongate mineral grains and stretched pebbles usually marks the primary direction in which metamorphic rocks have been extended by flow. In local adjustment zones separating masses that have extended different amounts, this lineation has been a direction of slip. Kinks and crumples resulting from this slip lie in secondary lineation directions transverse to the primary mineral lineation.During deformation relatively mobile materials move into dilatant zones caused by irregularities in primary flow directions. This secondary movement transverse to lineated, primary-flow directions is the cause of crenulations and folds with axes parallel to flow lineations.INTRODUCTIONThe arrangement of inequidimensional particles in rocks is rarely statistically random. Platy minerals tend to be parallel to bedding and foliation planes. Elongate particles and linear structures lie most frequently in certain lineation directions. The types of elongate particles in lineated rocks include needle and blade shaped mineral grains, sheared out segregations, and stretched pebbles, amygdules, and aolites.Crenulations and kinks are the most common of the linear structures involved.Faint lineations are readily overlooked. Even strong lineations have been ignored. This is unfortunate as even weak lineations may be important.Use of lineation information Well-developed lineations influence the mechanical properties of rocks. Quarry workers have long known that the mechanical properties of rock masses vary directionally...

Jan 1, 1965

By Rolf S. Paine

The Bureau of Mines studied the presplitting technique used for control-ling overbreakage in the walls of a vertical shaft at the U.S. Army Corps of Engineers Littleville Dam project near Huntington, Mass. The periphery of the shaft, the dimensions of which were 16-1/2 feet wide by 21 feet long and 52 feet deep, was presplit (cracked) in the solid to a depth of 48 feet prior to full-depth sinking. Presplitting prevented overbreak in a fairly soft schist and provided sound self-supporting walls which required very little scaling.

Jan 1, 1965

By J. B. Morgan

The mechanical behavior of MgCu2 from 20 o to 725°C has been determined by "brittle-ring" tensite-test techniques, axial compression, and bending experiments. Compressive ductility begins at 450°C (0.65 T/Tm) and slowly increases with increasing temperature white the tensile ductility is characterized by an abrupt brittle-ductile transition at 600°C (0.8T/Tm). The compressive strength increases eightfold from room temperature to 400°C with a "normal" decrease as the temperature is further increased. The tensile strength goes through a rather abrupt threefold increase above 600°C with a subsequent decrease at higher temperatures. The slip system is (111)[110] and the twinning system is (111)[112]. At high temperatures MgCu2 is quite rate-sensitive, and dynamic yield points are observed that are extremely orientation-dependent. The high-temperature creep behavior under constant load is characterized by an increasing strain-rate with time. The general characteristics of the mechanical behavior make it possible to classify MgCu2 with those materials in which initial mobile dislocation density and the dislocation velocity-stress dependence are significant in determining mechanical response. Mgcu2 is the C15 prototype of the cubic Laves phase. Its range of homogeneity extends from 32.8 to 35.5 at. pct Mg at 500°C and narrows at lower temperatures. The lattice parameter is reported to vary from 7.02 to 7.05A,1 and the compound is completely ordered to the melting point of 819°C. MgCu2 has a brassy metallic appearance, is extremely brittle, and many of its physical properties are intermediate between those of the constituent elements: the electrical resistivity is 3.5 x 10-6 ohm-cm, Young&apos;s modulus is 10x 106 psi, the shear modulus is 6 x l06 psi, and the thermal coefficient of expansion is 18.7 x 10-6 cm per cm per "C from 20" to 250°C. Usually, properties of intermetallic compounds as functions of temperature have been determined by hardness, compression, or impact behavior, and almost all of these experiments have been performed on polycrystalline materials. Tammann and Dahl,2 for instance, determined the onset of ductility in a series of binary intermetallics by ball-hardness measurements and found the onset to range between 0.71 and 0.96 T/T,. Lowrie&apos;s3 investigations included some tensile properties, and he found ductility beginning around 0.65 T/Tm for most materials examined. His work did include some data on polycrystalline, nonstoichiometric MgCu2, however. The present work is an attempt to extend the examination of the particular compound MgCu2 in single-crystal form in order to aid the formation of general concepts about mechanical be-

Jan 1, 1965

By B. B. Sandiford

It has been known for many years that the efficiency of a water flood can be improved by lowering the water-oil mobility ratio in the system. Such a change leads to better sweep efficiency and also to more efficient oil displacement in the swept zone. Data from our laboratory water-flood tests of both small cores and long sand packs are presented which show that water mobility can be reduced and oil recovery increased by the addition of certain polymer solutions to flood water. The reduction in mobility, in many cases, is greater than would be expected from conventional viscosity measurements. These solutions, however, do not cause significant reductions in oil mobility. The over-all effect of these mobility changes is increased waterflood oil recovery. Encouraged by results of our laboratory work, we expanded our study to include pilot field tests of floods with such solutions. One such test, made in the West Cat Canyon field, Santa Barbara County, Calif., is described in detail in this paper. Three other field tests are also discussed. INTRODUCTION Oil production from most reservoirs following primary depletion and/or water flooding is often less than 50 per cent of the original oil in place. Heavy oil reservoirs seldom yield over 15 per cent of their original oil. With new reservoirs becoming harder to find, the improvement of oil recovery efficiency is one of our very important problems. We describe here some of our attempts to increase the efficiency of oil displacement by adding a water-soluble polymer, partially hydrolyzed polyacrylamide, to flood water. This technique will be termed "polymer solution flooding". The concept of using high-viscosity water to increase the efficiency of water flooding is not new. In 1944 Detling (Shell Development Co.) obtained a patent covering the use of several additives for viscous water flooding.&apos; His objective was to improve water-oil mobility ratios by increasing the viscosity of the flood water. Other patents2-27 have been granted covering specific water-SO~LIble polymers or specific conditions of viscous water flooding. Barnes&apos;" described his laboratory model study of the injection of a viscous water slug into a reservoir which had been partially invaded by bottom water. He concluded that, for this type of reservoir, "the cost of viscous water should not exceed a few cents per barrel for viscous water slug injection to be economically feasible" Our studies have led us to a somewhat different conclusion in a number of cases where hydrolyzed polyacrylamide solutions have been injected into reservoir models or actual reservoirs. Possible reasons for this difference are discussed in this paper. Our studies have shown that polymer solutions may lead to an increase in oil recovery over that from an ordinary water flood by (1) improving sweep efficiency, (2) improving microscopic displacement efficiency, or (3) a combination of these mechanisms. In the work of Barnes, only the benefit of improved sweep efficiency was considered. Also, our work has shown that there are marked differences in the effectiveness of different water-soluble polymers as flood water additives. Partially hydrolyzed polyacrylamide is better than many other water-soluble polymers we have tested because, even in very low concentrations, it can lead to increased oil recovery. This is an important advantage when either a dilute polymer solution is injected continuously or a relatively concentrated slug is injected followed by water. In the latter case! portions of the slug become diluted and function in the formation as very dilute solutions. As dilution takes place the effective slug size will increase which, in turn, will reduce the cost per barrel of the effective flooding medium. The reason that partially hydrolyzed polyacrylamide solutions are more efficient at low concentrations than certain other polymer solutions of equivalent viscosity (when measured in conventional viscometers) is not fully understood. We do know that the shapes and sizes of macro-molecules dissolved or suspended in liquids influence the flow properties of their solutions or suspensions. Solutions of partially hydrolyzed polyacrylamide cause greater reductions in water mobility than would be expected from conventional viscosity measurements. LABORATORY STUDIES Laboratory water floods were run in linear and radial systems with different water-soluble polymers and under varying conditions of flow. including reservoir conditions of temperature, pressure and fluid composition. Some of these runs are considered in this section. OIL DISPLACEMENT IN LINEAR MODELS In this group of runs the sweep efficiency approached 100 per cent because the linear sand packs used were as nearly uniform as possible. Results reflect primarily the micro-scopic displacement efficiencies. The laboratory models were unconsolidat-ed sand packs the lengths of which varied from about 4 in, to 40 ft. Further information on the flow models used is listed in Table 1. Using conventional procedures, water floods were run on sand packs containing either refined or crude oil at restored state. Frequently, a repeat run, similar to the first, was made as a check. Then a third run was made on the restored-state model using either polymer solution or a combination of polymer solution (slug) and water. Details of these runs are also reported in Table 1. In Figs. 1 and 2 results of two different groups of runs are shown in which the oil used was a 62-cp refined oil and the flooding medium

Jan 1, 1965

By L. F. Mondolfo, W. T. Collins

A study of the relationship between undercooling for nucleation and structure in Sn-Cu alloys with 0.1 to 5 pct Cu has shown that in hypereutectic allojls the halo of tin that surrounds the primary crystals of Cu3Sn5 is larger, the larger the undercooling for nucleation o,f the tin. This increase of halo size results in a decrease of coupled eutectic, and, in alloys far from the eulectic composition, may produce its complete disappeavance, with the formation of a divorced eutectic structure. This was confirnred by the excrrnination of other alloys in which divorced eutectic slructuves are formed, and leads to the conclusion that they ave only an extrenle case of halo forrtzalion , which results when the two phases freeze one at a time and solidification of the first is completed Defove the second starts. It was also found that under proper conditions of nucleation all types of eutectic structures can be formed in the sartte system , and therefore divorced eutectics, like normal and anomalous, are not characteristic of the syslett~, but are mainly controlled by nucleatiorz. Dizlovced eutectics are formed when the phase that tutcleates the eulectic vequires a large undevcooling for ils nucleation and when the cotnpositiorz of the alloy is far from the eutectic., on the side of the primary phase that does not nucleate the other phase. It is recommended that the tevm "divorced" be used in preference to degenerate because it is more desct-iptice of the morphology and mode of forinalion of the structures. ThE variety of structures found in eutectic alloys has been extensively investigated and classified. The most accepted classification is the one by ~cheil,&apos; in which three different types of eutectic were distinguished: 1) normal, 2) anomalous, 3) degenerate (divorced). ATornlal eutectics are typified by the simultaneous growth of the two phases ("coupling") by which the two phases appear as interpenetrating crystals. The presence of a crystallization front, in which the two phases grow side by side, creates the eutectic grains, with the boundaries where the fronts meet. The presence of eutectic grains is the .distinguishing feature of a normal eutectic, according to Scheil. Straumanis and Brakss2 examined the Cd-Zn system and showed that there was a crystallographic relationship between the phases. Later, others4 also investigated additional systems and found definite crystallographic relationships in the coupled eutectics. The anornalous eutectic shows much less coupling than the normal; the two phases are intimately mixed but &apos;grow without a uniform crystallization front—a consistent crystallographic relationship— and the eutectic grain is conspicuously absent. As in the normal eutectics faster rates of growth result in a finer structure, but there is not the typical uniform spacing of normal eutectics. The degenerate eutectic shows no coupling; in fact the two phases attempt to minimize their area of contact and to form separate crystals. It has been suggested5" that slow cooling may favor this type of structure. Scheil believes that normal eutectics are formed when the two solid phases are present in more or less equal proportions, whereas both anomalous and degenerate eutectics form when one of the phases is present only in small amounts. spengler7 extended much farther this qualitative relationship between the eutectic type and the ratio of the two phases, and added a relationship to the melting point of the constituents. On this basis he proposed two equations for determining into which of Scheil&apos;s classifications an alloy belongs. The first equation is: where TI is the melting temperature of the lower-melting component, Tp of the higher-melting component, and Te the eutectic temperature. The second equations is: where is the volume percent of the lower-melting phase and $2 of the higher-melting phase at the eutectic composition. If 0 and/or 4 are in the range 0.1 to 1, a normal eutectic is formed; if in the range 0.01 to 0.1, anomalous; if less than 0.01, degenerate. Although the examples given by Spengler show a good agreement with the formulas, chadwick found that the Zn-Sn eutectic is normal to all growth rates, even though the volume ratio is 12/1, and Davies9 reports that the A1-AlgCo2 eutectic is normal, with a volume ratio of more than 30/1. Many more discrepancies of this type can also be found. Neither Scheil nor most of the other investigators have considered nucleation as a factor in the formation of divorced eutectics. Daviesg states that divorced eutectics form when neither phase acts as

Jan 1, 1965

By J. E. Warren

In their analysis of Eqs. 29 and 30, the authors correctly deduce the following behavior limits for the "differential capacitance model". 1. When the rate group a is sufficiently large, the model reduces to that implied by Eq. 1, i.e., the simple convection-diffusion model. 2. When the rate group a is sufficiently small, the model reduces to that implied by Eq. 1 with 1 replaced by 1, i.e., the simple convection-diffusion model with a total pore volume equal to that occupied by the mobile fluid in the original model. Unfortunately, the authors&apos; solution, Eq. C-1, to the transformed versions of Eqs. 29 and 30 does not exhibit the same limiting behavior. For example, as a approaches zero, Eq. C-1 reduces to the solution to Eq. 1 or, equivalently, the solution to Eqs. 29 and 30 for sufficiently large values of a. Therefore, it can be concluded that Eq. C-1 is not a general solution to Eqs. 29 and 30; this conclusion can be easily verified by substitution. I suggest that the correct form of Eq. C-1 is the following: It is generally realized that accounting for dispersion effects is an extremely tricky business; therefore no one should criticize the pragmatic approach of Coats and Smith who proceeded by accessible theory, made use of some available phenomenology, and who then took the trouble to check the consequences, against their own carefully undertaken experimental results. Here I should like to defend three assertions: (1) Coats and Smith copy the error of previous authors in the formulation of the so-called simple diffusion model (which error is then retained in their differential capacitance model); (2) improving the fit between data and the predictions of an arbitrary model by increasing the number of parameters is a triviality unless the parameters are disposable by being independently determined; and (3) existing experimental procedures lack sufficient resolution to clarify some current theoretical uncertainties. Taking first the view that all theoretical approaches (whether constructed by statistical, finite difference, or continuum arguments) tend to reduce to the same model form as fixed by the number and nature of the disposable parameters, one notices that the "finite-stage" model of Deans1 is equivalent to the Coats and Smith so-called differential capacitance model for the pertinent case where a

Jan 1, 1965

By R. W. Smith, T. J. Smolik

Recent work indicates that fluosilicate ions and or fluosilicate amine complex ions play important roles in fluoride activation of bery and feldspars in cationic flotation systems. In an attempt to further confirm conclusions reached in this earlier work, an infrared and X-ray diffraction study of the action of fluorides in cationic flotation of silicates was undertaken. It should be noted that in recent years considerable use has been made of infrared spectroscopy in studies of surface phenomena,2-4 and these studies have established the excellence of the technique. In the present study infrared spectra were obtained for various products of the reaction of HF and dode-cyclamine hydrochloride with quartz, microcline and beryl. These spectra were compared with one another and spectra of several inorganic and organic substances. In addition to infrared spectra, X-ray diffraction patterns were run on many of the reaction products obtained. A model 137 B Perkin Elmer Infracord double beam spectrophotometer containing sodium chloride optics was used to obtain the spectra. Infrared samples, except for the dodecylamine sample, were prepared by thoroughly mixing the substance to be analyzed with purified KBr in steel vessels on a Wig-L-Bug amalgamator. One-half in. pellets weighing 100 mg were than pressed under vacuum. Details concerning percentage of the substance to be analyzed in the pellets are indicated on the spectra. In all cases except for dodecylamine a KBr pellet was placed in the reference beam of the spectrophotometer to cancel bands due to possible impurities in the KBr. The dodecylamine sample on which an infrared spectrum was obtained was prepared by placing pure dodecylamine between two salt plates. X-ray diffraction patterns were obtained with a Norelco instrument, using a copper target tube, nickel filter and Geiger tube detector. The samples were ground into powders and either placed on glass slides with glue or placed into regular powder sample holders for diffraction studies. Goniometer scanning speed varied from 1°/min to 1/8°/min. EXPERIMENTAL RESULTS AND DISCUSSION Infrared spectra of microcline, beryl and quartz were obtained first and are shown in Fig. 1. These spectra agree reasonably well with previously reported spectra.5,6 The microcline (Fig. 1 a) and beryl (Fig. 1 b) were from good Black Hills crystals. The quartz (Fig. 1 c) was from a large, clear Brazilian crystal. It is not clear whether absorption bands of minerals are due to molecular vibrations, lattice vibrations or both. Fig. 2 shows infrared spectra of dodecylamine (Fig. 2 a) and dodecylamine hydrochloride (Fig. 2 b). The dodecylamine spectrum checks quite closely with that reported in Sadtler.8 Little is known of the spectra of hydrochloride salts of amines,9 and a spectrum of dodecylamine hydrochloride could not be

Jan 1, 1965

By H. P. LeVan

Research was conducted to examine the feasibility of extracting manganese from Georgia umber ore by a three-stage continuous sulfuric acid-ferrous sulfate pickle liquor leaching process. A continuous cyclic process for treating the umber was operated successfully, using a synthetic solution simulating a ferrous sulfate fortified anolyte solution discharged from a manganese electrolytic cell as the leaching medium. Leaching efficiency based on removal of the manganese from the ore ranged from 83 to 89 percent for all systems tested.

Jan 1, 1965

By McIntosh A. H, Torlach J. A

Since the last paper on mining methods was presented to the Annual Conference of the Australasian Institute of Mining and Metallurgy in 1:960, numerous advances have been made in drilling and blasting techniques at Mount Morgan. This paper describes the drilling and blasting methods being employed in the open cut. The change over to track mounted percussion drills for all types of primary drilling is almost complete and new techniques such as detergent drilling and pressure loading of ANFO are being applied successfully.

Jan 1, 1965

By M D. Winning

The historical development of the elemental sulphur recovery industry in Western Canada is reviewed for the period 1952 to 1965. A brief technical description of a typical modified Claus sulphur recovery unit is presented. Some predictions are made concerning the future of the elemental sulphur recovery industry in Western Canada. THERE are evidences of sulphur or its compounds having been used for religious and medicinal purposes as far back as we have a recorded knowledge of history. As typical examples, sulphur was burned as a sort of inverse incense to drive away evil spirits at religious festivals, sulphur ointments were used by the early Egyptians to cure eye ailments, and hot sulphur-spring water was used as a cure for a variety of ailments. Thermopyle was called "Hot Gates" be-cause of its fame as a spa as well as a mountain pass. The Romans discovered the sulphur deposits in Sicily and mixed sulphur with bitumen for incendiaries; and, of course, anyone familiar with the travels of Marco Polo knows about the Chinese development of gunpowder, which contains sulphur. In some aspects things haven&apos;t changed much today. We still use sulphur-bearing ointments, and we still use the hot sulphur springs such as the one at Banff in Western

Jan 1, 1965

By D. Havlena, A. S. Odeh

The use of the straight-line method of solving the material balance equation is illustrated by means of six field cases. Also, the application of statistical criteria to arrive at the most probable answer is shown. The theory underlying the straight-line method of solution and the applicability of the statistical criteria was presented in a previous paper.&apos; The field cases include saturated and undersaturated oil reservoirs with and without water drive. The aquifers discussed are: limited radial, infinite radial, very small aquifer and infinite linear. The field cases also include a gas reservoir producing under water drive. INTRODUCTION In a previous paper,&apos; the authors presented the theory underlying the solution of the material balance as an equation of a straight line. The appropriate equations for various material balance cases as well as the methods of analysis and interpretation with comments and discussion were also included. To illustrate the various theoretical cases treated previously, five field cases are analyzed in this paper by employing the straight-line method of solving the material balance equation (MBE) and one example previously published is referred to. The use of statistical criteria to arrive at the most probable answer is also shown. All the field examples presented, except Case 2, are excerpts from complete reservoir studies. To illustrate the method, only sections specifically dealing with the material balance principles are included. Additional geologic information and basic data are reported to better acquire an understanding of the cases and thus to better follow the reasoning that suggested the successful application of the straight-line method of solving the MBE. The six cases are: (1) saturated reservoir, small gas cap, limited aquifer; (2) saturated reservoir, very small gas cap, infinite aquifer; (3) undersaturated-saturated reservoir, very small aquifer; (4) highly undersaturated reservoir, no water drive; (5) high undersaturated one-well reservoir, limited aquifer; and (6) gas reservoir, infinite linear aquifer. THE D4 SAND, GUICO FIELD, VENEZUELA The D, sand, which was discovered in 1943, is presently in a depleted state. Since its discovery it has produced under water drive, gas-cap-gas expansion, and solution gas drive. In Nov., 1947, water injection was initiated to arrest further pressure decline. When discovered, the D, sand was a saturated reservoir with a gas cap /oil zone volume ratio m estimated volu-metrically at 0.0731, an average permeability of 500 md, a porosity value of 25 per cent, and an oil viscosity at reservoir conditions of 0.3 cp. The volumetrically determined stock-tank oil initially in place was 23.1 million bbl. The volumetrically weighted physical data and production data available until Nov., 1953 are reported in Table 1. In Ref. 1, the effects on the straight-line plot of various values of ro/r for a constant ?to, or of various dimen-sionless times for a constant r8/r10 were theorized and were illustrated in Fig. 3A of that reference. In this field case, the previously theoretically predicted effects are established. Thus, the MBE calculations using Eq. 3c of Ref. 1 were performed for various r6/r10 and dimension-less time values. Eq. 3c of Ref. 1 is:

Jan 1, 1965

By Tasuku Fuwa, John Chipman, David H. Kirkwood

Fe-C-Si alloys in silica crucibles were held at 1600°C in a controlled atmosphere of CO and Co2 and the approach to equilibrium was obsertsed. Results were not of sufficient precision to establish the activity and interaction coefficients. Observations 012 the equilibrium provided an average value for the standard free-energy change which differed by + 1.1 kcal from the earlier accepted value. The C-SL relation at other temperatures is calculated and shown graphically. IN the refining of steel in an acid-lined furnace, it is well known that, unlike in basic refining, a very significant amount of silicon may remain dissolved in the metal even when the carbon content approaches a final endpoint. Further, it is known that the residual silicon increases with increasing temperature. The quantitative relation between silicon and carbon can be calculated for equilibrium conditions from data already available on the Fe-C-O and the Fe-Si-O systems. Such equilibrium calculations could show us approximately the limitations within which the reaction would be expected to operate in practice. In the oxidation of a bath containing both carbon and silicon it is well known that at low temperatures silicon is preferentially oxidized first. It can be shown by calculation that at high temperatures carbon will be oxidized preferentially. It is the purpose of this paper to record direct observations on the Si-C relation by means of experiments carried out in an atmosphere of carbon monoxide for Fe-C-Si alloys contained in silica crucibles. When such a system is brought into equilibrium, at a fixed temperature, the composition of the liquid metal is governed by the following equations: Both K1 and K2 are known with a fair degree of accuracy, and may be calculated from the tabulated In general the percentage of CO2 is extremely small compared to that of CO and in the experiments to be described the partial pressure of the latter was generally only slightly below 1 atm. EXPERIMENTAL METHOD The induction furnace employed was the same as that described by Rist and chipman&apos; and by Fuwa and chipman.2 It was modified slightly in view of the change from alumina to silica crucibles. The small silica crucible was surrounded by a thin susceptor of molybdenum sheet which in turn rested inside a zirconia crucible. Since the zirconia was subject to breakage, it was supported inside an alumina crucible. The charge consisted of 30 to 35 g of electrolytic iron along with the required amounts of refined silicon and graphite to produce a melt of required composition. Purified carbon monoxide and carbon dioxide were passed into the furnace through carefully calibrated flow meters. Two separate and independent series of experiments were carried out. In Series I (D.H.K.) the melt was held in the furnace at 1600°C for periods of time up to 6 hr. Samples were taken at intervals in silica tubes and were analyzed for carbon and silicon. The results of the last one or two samples taken from each experiment and the direction in which equilibrium appeared to be approached are shown in Table I. In Series II (T.F.) the silica crucibles were of less satisfactory strength and the melts were held at 1600° C for periods of only 2 to 4 hr. In heats number 29 to 45 inclusive, the metal was cooled in the furnace and the ingot itself served as a sample for analysis. In heat 46 and all subsequent heats, samples were withdrawn in silica tubes at the termination of the heat, and these samples were analyzed. The results of all of these experiments in which equilibrium appeared to be approached are listed in Table II.

Jan 1, 1965

By M. Cohen, P. E. Beaubien, D. Caplan

Addition of 1 pct Mn to Fe-26 CY ca/(ses a12 increase in scaling rate at 870° and 1090°C. Whereas only the rhombohedral oxide, formrs on tire manganese-free alloy, with manganese present major amounts of the spinel .Mn0 . Pro-duced through which diffusion is more rapid. At 1090°C the scale formed OH Mn is highly, irregular due to blistering and sintering, This is a second cause of faster oxidation Since much of the blistered oxide does not participate as part of the protective layer. The oxide phases that form at different times depend on the degree to which the surface metal has become depleted, in manganese by preferential oxidation. PREVIOUS work has demonstrated that the oxide scales formed on chromium steels at high temperature consist of both spinel and rhombohedra1 phases and may contain considerably more manganese, especially in the spinel phase, than is present initially in the alloy.&apos; It has further been observed that a binary Fe-26 Cr alloy scaled less rapidly than an equivalent commercial steel and formed no spinel.&apos; However, it is not established if manganese in chromium alloys actually promotes formation of spinel nor if it affects oxidation resistance. It seemed expedient to try to evaluate the specific effect of manganese by oxidizing an Fe-26 Cr alloy containing a small manganese addition under the same experimental conditions as used for the manganese-free alloy.&apos; EXPERIMENTAL Table I shows the composition in weight percent of the Fe-26 Cr-1 Mn alloy and of the Fe-26 Cr alloy used as reference. The alloy with manganese was prepared from the vacuum-melted Fe-26 Cr alloy by remelting in vacuum with the proper manganese addition. The ingot was rolled to strip and specimens 1.1 by 0.035 by 5 cm and 1.1 by 0.5 by 4 cm cut out or machined. As previously described2 the specimens were smoothed by abrading through 600-grit Sic paper, electropolished in acetic-perchloric acid (20 to 1) to remove 10 p of metal, annealed at 1100°C in 20 torr of purified argon, and electropolished to remove a further 10 p of metal. They were then either rinsed in water and methanol and blotted dry or immediately etched for 45 sec in deoxy-genated 4 N HC1 under cathodic polarization at 10 pa per sq cm. Oxidation runs were carried out in a vertical tube furnace in a flow of purified oxygen at 1 atm while the weight increase was recorded continuously on a* automatic balance.3 Alter 98 hr at 870.C or 20 hr at 1090"C the specimens were removed to flowing argon and observed microscopically for evidence of spalling as they cooled. Subsequently they were examined by X-ray diffraction, the oxides analyzed chemically, and metallographic cross settions prepared. RESULTS Figs. 1 and 2 show the oxidation curves of Fe-26 Cr-1 Mn at 870&apos; and 1090C. The Fe-26 Cr reference runs are shown as dashed curves. Experimental details of the six runs are included in Table 11. The first 20 hr of run 1 is repeated in Fig. 2 to show the effect of temperature. At 8&apos;70°C the weight gain for Fe-Cr-Mn is about twice that of Fe-Cr (curve 1 vs curve 2, Fig. 1). Both alloys show regular oxidation curves. On parabolic coordinates (right-hand scale of Fig. 1) the

Jan 1, 1965

By H. Siebel, N. A. D. Parlee

MIZIKAR, Grace, and parlee&apos; studied rates of absorption of oxygen in stagnant liquid silver in a new type of open-ended gas-liquid metal diffusion cell, where the capillary diameters used were 1.5, 2, and 3 mm. They reported that the rates appeared to be controlled by the rate of diffusion of oxygen atoms in liquid silver and they used their data to arrive at the following equation as a reasonably good representation of the diffusivity (D) of oxygen in liquid silver: D = (14.7)10-4 exp (-7100 ± 3200)/RT cm2/sec Since this type of diffusion cell offers a promising method of measuring diffusivities of gas atoms in liquid metals, the senior author of this note and his students are carrying on a critical examination of the method, and are attempting to improve and extend the technique. The research reported briefly here was designed to examine more carefully the earlier conclusion1 that the absorption rate is diffusion-controlled, and to find out whether the diameter of the cell could be greatly increased and thus extend the method to systems where gas solubilities and diffusion rates are much smaller than in the case of oxygen in silver. For the purpose of these experiments, the open-ended capillary cell used by Mizikar, Grace, and Parlee was replaced by a small cylindrical crucible (1 to 1.7 cm in diam) containing pure silver (to a depth of 1.3 to 3 cm) resting in the bottom of a closed-ended vertical quartz tube, with an evacuated quartz filler tube just above the crucible to reduce dead volume. The method of measuring the rate of absorption was otherwise very similar to that of Mizikar, Grace, and Parlee and all the same precautions were taken. A much smaller and shorter tube furnace was used for heating, but simi- lar precautions about temperature gradients were observed. This technique was nothing more than the application of a Sieverts apparatus to the measurement of rates of absorption in small crucibles of stagnant liquid silver. In each run the volume of gas absorbed (V) was plotted against the square root of time (vt) and apparent diffusivities were calculated from the slope of the line, as described by Mizikar, Grace, and parlee.&apos; Care was taken to use only the data obtained during the early part of the total absorption period while the cell functioned as one of infinite depth. The results at 1000°C are summarized in Table I and Fig. 1. The following conclusions may be drawn: 1) Diffusion cells up to 1.7 cm in diam yield, within experimental error, the same values for the diffusivity of oxygen (D) as the capillary cells of 1.5, 2, and 3 mm in diam employed by Mizikar, Grace, and Parlee. Cell diameters as large as 1.7 cm are probably not desirable for the most precise work. Intermediate sizes, perhaps 0.5 cm, will be most practical. 2) All absorptions measured were consistent with a model where the rate is controlled by the diffusion of gas atoms in the metal. The fact that runs at absorption pressures ranging from 0.1 to 1 atm (at any one temperature) give

Jan 1, 1965