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By Edwin Ludlow

To THE members of the American Institute of Mining and? Metallurgical Engineers who were fortunate enough to be able to attend the Fiftieth Anniversary at Wilkes-Barre, it was brought home that commercial anthracite requires not only expensive mining but that the milling or preparation of it is also a costly operation, requiring very large capital expenditures and high maintenance and labor costs. The great trouble that coal men meet in discussions of coal problems today is the difficulty the average coal user, especially in the East, finds in distinguishing between anthracite and bituminous coals. They are two entirely separate problems and yet the people who are burning coal complain bitterly of the high cost of anthracite and quote the figures furnished in regard to the prices of bituminous coal and feel that the anthracite operators are making an excessive profit, without realizing the enormous difference in the cost of production in the two fields. The great difference that can be marked is that in this year of industrial depression the prices of anthracite have been not only maintained but have increased during the summer, while the price of bituminous coal has been continually dropping since the first of the year, and yet the same law of supply and demand governs both anthracite and bituminous. In order to understand the situation the two problems must be considered from their separate points of view.

Jan 1, 1921

By H. H. Rachford

Numerical solutions of immiscible flow problems in which dispersive effects of capillarity are dominated by convection require excessively fine grid spacing with attendant high computing costs. The use of coarser spacing reduces cost but often produces oscillation or undue dispersion associated with displacement fronts, A numerical formulation is proposed here which should be applicable to two-dimensional flow problems. it is in part analogous to an approach previously tested for miscible systems. The convective transport is approximated using a change of variables to yield a coordinate system moving approximately with the local characteristic velocity. The capillarity-induced dispersive terms in the differential system describing the process are approximated with respect to a fixed coordinate system by the usual implicit formulation. One-dimensional tests of the procedure yielded results in which the saturation profiles tended smoothly to the zero-capillary pressure solution as the ratio of viscous to capillary forces was successively increased in a sequence of calculations. This contrasted favorably with solutions by other numerical procedures which would require attendant grid refinements to approach the zero capillary pressure results. INTRODUCTION Numerical solution of displacement problems has until recently relied on applying methods developed primarily for transient heat-flow problems. Such problems are classified as parabolic in type, and where the heat transport is purely by diffusion their solutions are characterized by a high degree of smoothness. It is not surprising, therefore, that for approximating these solutions available finite difference methods are quite adequate. In flow problems the transport is partly by diffusion, partly by convection or flow. Although the problem remains of parabolic type because the dispersive effects of capillary forces or diffusion play some role in every displacement, at high flow rates the problem is dominated by convection, and solutions tend toward those of equations of the hyperbolic type. Solutions of hyperbolic problems are characterized by the translation of fronts, or discontinuities, that may progressively increase in sharpness. Numerical methods for treating parabolic problems become less and less satisfactory as displacement rates increase and the role of dispersion due to concentration or capillary pressure gradients becomes small relative to transport due to flow. In computation the difficulty manifests itself as an error associated with the grid size chosen. 1-6 In summary, if the heat-flow type approximations are to include the terms arising due to convection, one of several choices may be made: (1) an upstream (to the direction of flow) approximation for the convection terms may be used; (2) a centered-in-distance (CID) approximation may be used; or (3) a recently developed approximation based on the theory of oscillation matrices may be chosen.6 The last appears to have significant promise for one-dimensional flow problems; its extendibility to two or three dimensions is an open question. In either of the first two approaches, a suitably small ratio of v&/D must be maintained, where v is the velocity, & is the grid spacing and D the effective dispersivity in the direction of flow. In the first choice, the approximation of the convective part is only first-order correct and errors introduced appear as a numerically induced dispersivity of magnitude proportional to v?x. In the CID choice, the approximation can be second-order correct, but the difference formulation fails to satisfy the maximum principle unless a condition on v?x/D is met. Practically, this means that for high flow rates oscillatory solutions may result in the neighborhood of a front unless exceedingly small grid intervals are taken. While the procedure proposed by Stone and Brian4 permits a less severe limitation to be placed on this ratio, ultimately the flow rates increase relative to the dispersivity the oscillation obtains. Further, extensions of their approach to higher dimensional systems may be attended by considerable

Jan 1, 1967

By William B. Plank

ENGINEERING students to the number of 73,269 had been enrolled in United States and Canadian schools on Nov. 5, 1945, but, as shown in the following tables, even this sizable number will not greatly remedy the 150,000 deficit reported by Vannevar Bush, director of the U. S. Office of Scientific Research and Development, to exist in the engineering and scientific man-power supply. These figures were received in advance from the Society for the Promotion of Engineering Education, and are given in detail in the January 1946 issue of the Journal of Engineering Education. Although the enrollment on Nov. 5 was an increase of 76% over the low of 41,632 in 1944-45, it was still 36% below the peak enrollment in 1941-42 of 115, 228. These figures include both undergraduate students and graduate students in the schools of the United States and Canada and are therefore comparable. As was to be expected, almost half of this enrollment is in the first or freshman year and 25% of the total are veterans. Also, 1,850, or about 2.5%, are women. A measure of the seriousness of the engineering graduate supply in these two countries is indicated by the trend of the number of first degrees that have been conferred during this period of scarcity:

Jan 1, 1946

By K. E. Brown, A. R. Hagedorn

Continuous, two phase flow tests have been conducted during which four liquids of widely differing viscosities were produced by means of air-lift through 1%-in. tubing in a 1,500-ft. experimental well. The purpose of these tests was to determine the effect of liquid viscosity on two-phase flowing pressure gradients. The experimental test well was equipped with two gas-lift valves and four Maihak electronic pressure transmitters as well as instruments to accurately measure the liquid production, air injection rate, temperatures, and surface pressures. The tests were conducted for liquid flow rates ranging from 30 to 1,680 BID at gas-liquid ratios from 0 to 3,-270 scf/bbl. From these data, accurate pressure-depth traverses have been constructed for a wide range of test conditions. As a result of these tests, it is concluded that viscous effects are negligible for liquid viscosities less than 12 cp, but must be taken into account when the liquid viscosity is greater than this value. A correlation based on the method proposed by Poettmann and Carpenter and extended by Fan-cher and Brown has been developed for 1¼-in. tubing, which accounts for the effects of liquid viscosity where these effects are important. INTRODUCTION Numerous attempts have been made to determine the effect of viscosity in two-phase vertical flow. Previous attempts have all utilized laboratory experimeneal models of relatively short length. One of the initial investigators of viscous effects was Uren1 with later work being done by Moore et al.2,3 and more recently by Ros.4 However, the present investigation represents the fist attempt to study the influence of liquid viscosity on the pressure gradients occurring in two-phase vertical flow through a 1¼-in., 1,500 ft vertical tube. The approach of some authors has been to assume that all vertical two-phase flow occurs in a highly turbulent manner with the result that viscous effects are negligible. This has been a logical approach since most practical oil-well flow problems have liquid flow rates and gas-liquid ratios of such magnitudes that both phases will be in turbulent flow. It has also been noted, however, that in cases where this assumption has been made, serious discrepancies occur when the resulting correlation is applied to low production wells or wells producing very viscous crudes. Both conditions suggest that perhaps viscous effects may be the cause of these discrepancies. In the first case, the increased energy losses may be due to increased slippage between the gas and liquid phases as the liquid viscosity increases. This is contrary to what one might expect from Stokes law of friction,' but the same observations were made by ROS4 who attributed this behavior to the velocity distribution in the liquid as affected by the presence of the pipe wall. In the second case, the increased energy losses may be due to increased friction within the liquid itself as a result of the higher viscosities. The problem of determining the li- quid viscosity at which viscous effects becomes significant is a difficult one. Ros4 has indicated that liquid viscosity has no noticeable effect on the pressure gradient so long as it remains less than 6 cstk. Our tests have shown that viscous effects are practically negligible for liquid viscosities less than approximately 12 cp. Actually there is no single viscosity at which these effects become important. These effects are not only a function of the viscosities of the liquids and of the gas but are also a function of the velocities of the two phases. The velocities in turn are a function of the in situ gas-liquid ratio and liquid flow rate. Furthermore, the role of fluid viscosities in either slippage or friction losses will depend on the mechanism of flow of the gas and liquid, i.e., whether the flow is annular. as a mist, or as bubbles of gas through the liquid. These mechanisms are also a function of the in situ gas-liquid ratios and the flow rates. It would thus seem that the best one could hope for is to determine a transition region wherein the viscous effects may become significant for gas-liquid ratios and liquid production rates normally encountered in the field. The viscous effects might then be neglected for liquid viscosities less than those in the transition region but would have to be taken into account when higher viscosities are encountered. There are numerous instances where crude oils of high viscosity must be produced. The purpose of this study has been to evaluate the effects of liquid viscosities on twephase vertical flow by producing four liquids of widely differing viscosities through a 1 % -in. tube by means of air-lift. The approach used in this study was as follows:

Jan 1, 1965

By M. W. Legatski, D. L. Katz

The best currently available description of the longitudinal mixing properties of a porous medium is an equation of the form which relates the effective longitudinal dispersion coefficient Dp to the molecular diffusion coefficient Do, the electrical resistivity factor F, the porosity <f> and a Peclet number. If the parameters dpa and m are determined for a porous medium of known porosity and electrical resistivity factor, then a dispersion coefficient may be estimated for a given flow rate and a given gas pair. A new method, featuring on-line gas analysis by thermal conductivity and on-line data reduction by analog computation, was developed and used to determine these mixing parameters for eight naturally occurring sandstones and two dolomite samples. The exponent m of the above equation was found to vary between 1.0 and 1.5. The characteristic length dpa in the above equation was found to vary between 0.25 and 1.9 cm, with an average value of 0.4 cm for sandstones. Measurements were made on two cores in which paraffin wax had been deposited by evaporation from a pentane solution. They indicated that the presence of an immobile phase such as connate water could increase the dispersion coefficients significantly. INTRODUCTION While the petroleum and chemical industries have studied the mixing of miscible liquids flowing in consolidated porous media and of miscible gases flowing in unconsolidated porous media, relatively little data have been presented to describe the mixing of gases flowing through consolidated porous media. Such data are of particular interest to the gas storage industry. For instance, the U. S. Bureau of Mines is storing large quantities of a rich helium-nitrogen gas in contact with a natural gas in a dolomite reservoir. Since the rich gas occupies only 15 percent of the total reservoir volume, it is essential that the extent of rich gas-natural gas mixing be predicted and understood as a function of rock properties, pressure and rate of movement. This investigation was concerned only with the determination of longitudinal dispersion coefficients. It is understood that a transverse dispersion coefficient, which characterizes mixing perpendicular to the direction of flow, may be an order of magnitude less than the coefficient characterizing mixing in the direction of bulk flow.5719 It should also be recognized that the use of any dispersion coefficient is in itself a simplification. It is necessary to assume that mixing in a porous medium may be characterized by the equation for flow in a single direction. A number of authors1 l8,19 have pursued the mixing problem, not in terms of the so-called "dispersion model" described by Eq. 1, but in terms of a "mixing cell model". This model supposes that a porous medium is constructed of a large number of small mixing chambers and that the concentration of the diffusing component within each mixing chamber is uniform. Fick&apos;s law (Eq. 1) assumes that there is no gross by-passing of one fluid by another, and that there are not stagnant pockets of gas in the system under consideration as discussed by Coats and Smith.8 These assumptions are not always valid for flow through porous media and it is important to recognize the limitations upon Eq. 1. The most serious limitation upon the assumption of Fick&apos;s law mixing in a porous medium is

By R. W. Heckel, R. E. Trabocco

The recovery process in 400 Monel filings was followed, principally, by using the Warren-Averbach technique of X-ray peak profile analysis. The deformation fault probability, a, was 0.006 in samples of unannealed filings. a , the twin fault Probability , was approximately 0.002 in samples of unannealed filings. Both a and 0 were found to "anneal out" at 600°F. The effective particle size and mzs strain increased and decreased in the (111) direction, respectively, with increasing annealing temperature. The actual particle size was found to be almost equivalent to the effective particle size. Tile small values of deformation and twin fault probabilities accounted for the similarity in values of the effective and actual particle sizes. Stored strain energy and dislocation density calculations based on rms strain decreased with increasing annealing temperature. The dislocation density decreased from 10" per sq cm in the unannealed filings to 10&apos; per sq cm in the partially re-crystallized filings. The square root of the dislocation density based on strain to that based on particle size indicated a random dislocation distribution in the unannealed filings. The dislocation arrangement changed to one with dislocations in cell walls with increasing annealing temperature. THE recovery processes which occur in metals are generally thought to be a redistribution and/or annihilation of defects.&apos; Investigators&apos; have shown that recovery processes can be characterized by X-ray line-broadening analyses. Michell and Haig4 measured the stored energy of nickel powder by calori-metry and found the value to be greater by a factor of 2.5 than that from X-ray data obtained by the Warren-Averbach technique.= Minor increases in particle size occurred up to 752°F (recovery), while above 752°F the particle size increased greatly due to recrystalliza-tion. X-ray microstrain values decreased between room temperature and 392"F, remained constant from 392" to 752"F, and decreased from 752°F to a negligible value at 1112°F. Faulkner developed an equation for calculating stored strain energy based on X-ray line-broadening data which gave a closer correlation of measured and calculated stored strain energy based on the data of Michell and Haig. The stored strain energy released during recovery is predominately dependent on the decrease in dislocation density which was p-enerated from cold work.7 Stored energy has been measured8 in alkali halides during recovery and recrystallization and 80 pct of the stored energy was found to be released during recovery. Dislocation distributions have been studiedg in a number of fcc metals by thin-film electron microscopy. Howie and Swann" found the stacking fault energy of copper and nickel to be 40 and 150 ergs per sq cm, respectively. ~rown" has pointed out that these stacking fault energy values should be corrected to 92 and 345 ergs per sq cm, respectively. The dislocation distribution of a metal is directly dependent on the stacking fault energy of the system. Metals of high stacking fault energy such as aluminum cross-slip readily and do not form planar arrays of dislocations. Metals of lower stacking fault energy such as stainless steels" do not cross-slip readily. Cold-worked nickel has been found to form a cellular dislocation structure after annealing.13 The relatively high stacking fault energy of nickel and copperlo to a lesser extent favor cellular structures of dislocations rather than planar arrays after deformation. The present study of recovery was carried out on a Ni-Cu alloy (Monel 400) to compare with prior studies for pure nickel and pure copper. X-ray line-broadening techniques were used to measure the effect of recovery temperature on rms strain and particle size and the results were compared with previous studies on copper&apos;4-&apos;7 and nickel., Calculations were also made on stacking fault probabilities, dislocation density, dislocation distribution, and stored strain energy as affected by temperature. EXPERIMENTAL PROCEDURE The nominal analysis of the Monel 400 used in this investigation was: 66.0 pct Ni, 31.5 pct Cu, 0.12 pct C, 0.90 pct Mn, 1.35 pct Fe, 0.005 pct S, 0.15 pct Si. The annealed material was cold-reduced in two batches, one 50 pct and the other 80 pct. It was originally planned to conduct line-broadening studies of these bulk samples; however, rolling textures that developed produced low-intensity peaks which were not suitable for line-broadening analysis. Filings were prepared at room temperature from both the 50 and 80 pct cold-reduced specimens, series A and series B, respectively, and were not screened prior to heat treatment or X-ray studies. Heating to the annealing temperature, 200" to 120O°F, was accomplished in a matter of minutes in a hydrogen atmosphere. Following heat treatment, some of the filings were mounted and polished for microhardness measurements with a Bergsman microhardness tester, using a 10-g load. A G.E. XRD-5 diffractometer using nickel-filtered Cum radiation was used to obtain all diffraction patterns. Only (111)- (222) line-broadenin data were used in the present study since the {400f peaks were too weak to use. The Fourier analysis of the (111) and (222) peak

Jan 1, 1969

By M. E. Wadsworth, W. H. Dresher, W. M. Fassell

HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.&apos; The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.&apos; National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 sphalerite,4 galena," and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,6 ho found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo++ in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit&apos;s construction and operation have been discussed elsewhere,&apos; only basic features and principles of operation will be discussed at this point.

Jan 1, 1957

By W. W. Smeltzer

The linear formation rates of wustite films have been determined over the temperature range 590° to 1030°C using a vacuum microbalance technique. These rates are dependent directly on the partial pressure of carbon dioxide, Activation energies for film and scale formation in carbon dioxide and oxygen atmospheres are equivalent to either the dissociation energies of carbon dioxide and oxygen, or the activation energy for the diffusion of cation vacancies in wustite. Of the metals, iron is the most widely used basic constituent of durable alloys despite its intrinsic property of converting at a relatively rapid rate to the oxides from which it is derived. This property has accounted partially for many investigations on the oxidation of iron at low and high temperatures. Interpretation of the results have been complicated by formation of multilayers containing the various oxide phases. To aid in elucidation of the oxidation kinetics, measurements have been carried out in this investigation on the growth of the wustite surface layer. There are several studies directly related to the objective of this investigation. The growth of multilayer scales has been demonstrated to be diffusion controlled in oxygen at atmospheric pressure over the temperature range 450" to 1200°C by Davies, Simnad, and Birchenall.&apos; To gain an insight into the diffusion mechanism, Himmel, Mehl, and ~irchenall&apos; determined the self-diffusion coefficients of iron in wustite, magnetite, and hematite. These results were used to evaluate the oxidation rates of iron and its oxides, taking as a basis the theoretical parabolic rate equation developed by Wagner., The evaluations were compared to experimental data and were shown to provide essential confirmation of this theory. Fischbeck, Neundeubel, and salzer4 have demonstrated that the oxidation of iron in carbon dioxide and other atmospheres at high temperature obeys a linear relationship. Because the Arrhenius temperature coefficients of the reaction rate constants changed at the A, point they concluded that the passage of iron into the oxide controlled the reaction. This viewpoint has been accepted by Benard and ~albot&apos; to explain the occurrence of linear rates in oxygen before the onset of diffusion-controlled parabolic oxidation. This basic premise of a rate-controlling reaction at the iron/oxide interface has been questioned recently by Hauffe and Pfeiffer.&apos; Since the formation of wustite may follow a linear or parabolic relationship depending on the pressure of the gaseous re-actant, they propose that linear oxidation is determined by a chemisorption reaction while parabolic oxidation is controlled by diffusion. As confirmation of this viewpoint, Hauffe and pfeiffer6 and Pfeiffer and ~aubmeyer&apos; have established that the linear scaling constants of wustite formation at 1000°C in carbon-dioxide or low-pressure oxygen atmospheres

Jan 1, 1961

By M. J. Hordon, M. A. Wright

ReCENT work has indicated that the substantial decrease in the rate of fatigue crack propagation for aluminum observed below a critical vacuum level can be attributed to the depletion of oxygen or water vapor from the vicinity of the fatigue crack opening.&apos; At reduced gas pressures, generally below 10-2 Torr with fatigue strain amplitudes in the range *1 to 2 x 10-3 and cyclic loading rates of 25 to 50 cps, estimated rates of oxide or hydroxide monolayer adsorption on newly formed crack surfaces can fall behind the actual rate of crack extension. Changes in the critical pressure required for the transition in fatigue behavior with changes in temperature, strain amplitude, and cyclic frequency can be interpreted from variations in the adsorption and crack growth rates.&apos;" Although the adsorption model generally appears to explain the enhanced fatigue resistance of reactive metals in vacuum, the specific adsorbing gas species and nature of the adsorption mechanism are uncertain. In addition to the direct dissociation and adsorption of O2 on the metal surfaces,3 the dissociation of H20 and subsequent adsorption of H ions have been advanced for aluminum alloys.4 The present note describes some measurements of the fatigue behavior of 1100 aluminum in reduced partial pressures of specific gases including O2, H2O, and H2 in order to provide additional experimental data. Cantilever-type specimens of 1100-H14 aluminum were fatigued in cyclic reverse bending at constant strain amplitude using a multispecimen vacuum apparatus and procedure described previously.&apos; After initial vacuum evacuation to 1 x 10-7 Torr, the appropriate gas species was bled into the system through a calibrated leak valve. The input rate was adjusted to maintain the desired pressure level under continuous evacuation, thus minimizing possible changes in gas composition during testing. High-purity input gases including 99.9 pct O2, 99.999 pct H 2, and water vapor from triply distilled H 2 O were used to provide residual pressures. Trace amounts of contaminant species were limited by passing the Oz and H 2 input gases through liquid-nitrogen-cooled copper coils prior to entry to the test chamber. Care was taken to repeatedly flush the gas lines and valves before testing to minimize the effect of adsorbed contaminants. Residual gas pressures in the range 10-6 to 5 x x3 Torr were monitored by an NRC ionization gage corrected for each gas species. In the higher-pressure range, 5 x 1CT3 to 5 x 10&apos; Torr, an NRC alphatron gage was used. In operation, eight simultaneous fatigue tests were conducted at a constant strain amplitude of *1.2 x 10 at cyclic bending rates of 25 and 50 cps to give an average fatigue life of 6.5x 105 cycles-to-fracture at standard atmosphere and 3.3 x 106 cycles in 1 x 10"7 Torr vacuum. Representative results for the effect of residual O2, H2O, and H2 contents on the fatigue life are shown in Fig. 1 for tests performed at 50 cps. It is apparent that the presence of either O2 or H2O gas in the system at partial pressures greater than 10"3 Torr was noticeably detrimental to the fatigue life. In contrast, the enhanced fatigue resistance typical of high-vacuum environments was retained with pure H 2 through the pressure range up to 1 Torr. For partial pressures of H2 gas above 1 Torr, the fracture life noticeably decreased. The critical Hz

Jan 1, 1969

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,&apos; Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,&apos; Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By AIME AIME

NOTWITHSTANDING the metropolitan appearance of M. L. Haider, the present Chairman of the Petroleum Division, he is not a native New Yorker, but was born at Mandan, N. Dak., Oct. 1, 1904. He began his travels at an early stage in life and after attending the University of Southern California for two years he spent two additional years at Stanford University and was graduated in 1927. After a few months as an analytical chemist for the Portland Cement Co. he became research engineer in the natural gasoline department of the Richfield Oil Co. where he remained for approximately two years before taking a position with the Carter Oil Co. in Oklahoma. He was chief engineer for this company for three years before being trans-

Jan 1, 1945

By L. F. Mondolfo

R301 is a clad aluminum alloy, composed of a core of a duralumin-type alloy clad with a magnesium silicide alloy. It differs from other well-known clad alloys in that the cladding and the core respond to the same heat-treatments. and therefore the cladding contributes appreciably to the mechanical properties of the material. In Table I are reported the compositions of the core and cladding alloy for the material used for the experiments. Table i.—Chemical composition of R~OI Used for the Experiments Element Core Cladding Cu........................ . 0.01 Fe......................... . 0.42 Si......................... 0. 0.71 Mg........................ . 0.99 Mn ........................ . 0.54 In clad aluminum alloys where the core contains copper and the cladding does not, at elevated temperatures the copper tends to diffuse from the core through the cladding. This fact is well known and many investigations have been conducted to determine the features of this diffusion. Most of those investigations cover materials clad with pure aluminum; the present investigation covers a material clad with an alloy. Since the cladding thickness on R~OI varies with the gauge, as shown in Table 2, several gauges were investigated. Material and Procedure he material used was sheet of the following gauges: o.o2~, 0.040, 0.064, 0.102, 0.170 Cut in pieces approximately 3 by 5 in., it was in the cold-rolled state and was soaked for increasing times at the following temperatures: glo°F., 940°F., 970°F. A Lindberg cyclone furnace was used for the experiments. The procedure was as follows: The furnace was started empty with controlling pyrometer set at the determined temperature. After the furnace had reached that temperature, it was run for some 20 to 30 min. empty, in order to allow the temperature inside to become stabilized. Then the first samples were introduced. A load thermocouple, with recording pyrometer, was connected with the sample of the heaviest gauge. About 10 min. was required for the material to reach temperature and the soaking time was counted from that point. After zoo min. soaking, the second group of samples was introduced without stopping the furnace. After 200 min. more, the third group of samples was introduced, and so on, until the last sample had been introduced. Every time the furnace was opened and new samples were added, a drop of temperature was registered by the thermocouple connected with the material

Jan 1, 1946

By L. F. Mondolfo

R301 is a clad aluminum alloy, composed of a core of a duralumin-type alloy clad with a magnesium silicide alloy. It differs from other well-known clad alloys in that the cladding and the core respond to the same heat-treatments. and therefore the cladding contributes appreciably to the mechanical properties of the material. In Table I are reported the compositions of the core and cladding alloy for the material used for the experiments. Table i.—Chemical composition of R~OI Used for the Experiments Element Core Cladding Cu........................ . 0.01 Fe......................... . 0.42 Si......................... 0. 0.71 Mg........................ . 0.99 Mn ........................ . 0.54 In clad aluminum alloys where the core contains copper and the cladding does not, at elevated temperatures the copper tends to diffuse from the core through the cladding. This fact is well known and many investigations have been conducted to determine the features of this diffusion. Most of those investigations cover materials clad with pure aluminum; the present investigation covers a material clad with an alloy. Since the cladding thickness on R~OI varies with the gauge, as shown in Table 2, several gauges were investigated. Material and Procedure he material used was sheet of the following gauges: o.o2~, 0.040, 0.064, 0.102, 0.170 Cut in pieces approximately 3 by 5 in., it was in the cold-rolled state and was soaked for increasing times at the following temperatures: glo°F., 940°F., 970°F. A Lindberg cyclone furnace was used for the experiments. The procedure was as follows: The furnace was started empty with controlling pyrometer set at the determined temperature. After the furnace had reached that temperature, it was run for some 20 to 30 min. empty, in order to allow the temperature inside to become stabilized. Then the first samples were introduced. A load thermocouple, with recording pyrometer, was connected with the sample of the heaviest gauge. About 10 min. was required for the material to reach temperature and the soaking time was counted from that point. After zoo min. soaking, the second group of samples was introduced without stopping the furnace. After 200 min. more, the third group of samples was introduced, and so on, until the last sample had been introduced. Every time the furnace was opened and new samples were added, a drop of temperature was registered by the thermocouple connected with the material

Jan 1, 1946

By R. D. Pehlke, J. V. Gluck

A study was made of&apos; the effects of up to five additional solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450" to 650°C. The experimental measurements were made in a multielectrode galvanic cell apparatus employing fused LiCl-KCl as the electrolyte. The solute additions included indium, lead, tin, cadmium, copper, silver, antimony, or gold. A range of positice and negative interactiotls with zinc was covered. The experinzer~tal observations were cowlpared with the activity coefficients calculated usitlg either Wagner&apos;s first-order Taylor series rnodel or a proposed second-order solution itrteraction model. hi general, the truncated first-order Taylor series proposed by Wagner gaue good results for "dilute" solutions (XBi > 0.90) contaitzing up to six solutes. The second-order model, which includes a second-order cross-interaction term, produced a slight improvement in predictions for solutions with XZn = 0.015 and a significant improvement for solutions with XZn = 0.050 hear the limit of Henry&apos;s law region). Seveval of the quaternary solutions studied contained a total solute content of 0.215 mole fraction, and fairly good success was achieved in predicting the activity coefficient 01- zinc. ThE study of thermodynamic interactions between dilute solutes in liquid metallic solutions has occasioned much recent interest. It is useful to recall in this respect that Wagner&apos;s well-known expression for the activity coefficient&apos; is a practical application of the problem of representing a given function, i .e., In ?, by means of a sequence of polynomials. No specific physical model of a solution is involved in its use. As suggested by Wagner, a Taylor Series is used to expand In ? about a point of infinite dilution with respect to all solutes. The partial differential coefficients of the series have been termed "interaction parameters". Various authors&apos;-6 have proposed formalisms for parameters, the definitions being designed to meet some specific experimental or physical condition. A usual assumption is that terms above first-order in the Taylor Series may be neglected. In that case, the logarithm of the activity coefficient is expressed as a linear function of solute concentrations. The resulting expression is presumed valid for any number of additional solutes as long as the solution can be regarded as "dilute". This assumption can be termed "the hypothesis of additivity". However, experimental tests of that hypothesis for quaternary or higher-order solutions have been extremely limited. Primarily such tests have been confined to studies of effects of added metallic elements on either the activity of carbon or the solubility of gases in liquid iron.7-13 The only known previous study of an all-metal system is the limited work of Okajima and pehlke14 on the effects of multiple solute additions on the activity of cadmium in liquid lead. The present investigation is a portion of the work to determine the effects of various solute additions on the activity of zinc in dilute solution with molten bismuth in the range 450" to 650C It was shown for such ternary solutions that second-order Taylor Series terms could be evaluated at the same time as first-order terms, with no additional experimentation required. A second-order solution model was described which, under certain conditions, is a rigorous representation of solute activity in a ternary solution. (In the sense employed in this paper, the term "model", as distinguished from "equation", is taken to mean an empirical correlation or formalism, but not a hypothetical physical system per se.) Presumably such a model could be extended to produce a better representation of In ? in solutions of even higher order. The feasibility of a generalized Taylor Series approach to solution interactions and inclusion of second-order terms also has been discussed recently by Lupis and Elliott in independent work concurrent with the present investigation. In addition, they discussed empirical means of estimating certain second -order coefficients.17 The utility of such solution models rests on the ability of a truncated series to represent adequately the experimental facts in multicomponent solutions. Questions that arise include: Do the second-order terms really make a significant contribution? How far away from "dilute" solution may such models be applied? Are the types and varieties of the additional solutes important? among others. In order to provide some answers to these questions, an experimental study was made of the effects of two or more additional solutes on the activity of zinc in dilute solution with molten bismuth. Comparisons were then made with calculated activity coefficients obtained using the previously determined ternary interaction parameters. INTERACTION MODELS As an example of the approach to defining activities in multicomponent solutions, consider the Taylor Series expansion for a quaternary system, i.e., three dilute solutes. Writing terms through second order, the result is:&apos;&apos;

Jan 1, 1968

By AIME AIME

THE 1944 Chairman of the Institute of Metals Division might be classed as metallurgically ambidextrous ; he is teacher of theory and practice of both nonferrous and ferrous metallurgy, and he is consultant on brass and on highspred steel. Arthur Phillips was born in Troy N.Y. and attended the New Haven Connecticut high school. Upon graduation he entered Yale, receiving a degree in metallurgy in 1913. At that time Professor Mathewson was starting his plan of &apos;"co-operation with the metal industries in metallographic work at the Hammond Laboratory of the Sheffield Scientific School, Yale University, and Arthur Phillip, became the first co-operative graduate student, working in the laboratory of the Bridgeport Brass Co., and receiving his Masters of Science degree in 1915. A little later, when the department of metallurgy at Yale was expanded. Me. Phillips was appointed assistant professor. In 1928 he was made associate professor, and in 1934 he was promoted to full professor.

Jan 1, 1944

By Frank Firmstone

The material described below was made at Furnace No. 2, Longdale, Va., Oct. 28, 1907, during a sudden derangement of working, in the course of which the furnace became entirely bridged over and for some time no solid material whatever descended into the hearth. This caused the hearth to become so completely emptied that, at the tuyere-level, a pricker put in at one tuyere could be seen by looking in at the opposite one. The tap-hole was opened and the iron got out with some difficulty. It ran sluggishly, throwing many sparks, but was not too thick to run into the chill-molds. Naturally, the product was assumed to be white iron, which is almost always produced under similar circumstances; but on removal front the molds it proved to be very strong and tough, although full of blow-holes. Most of these blow-holes bad bright, unoxidized walls. The iron could be drilled by using a "special steel" drill, the drillings curling up similarly to those of steel. An analysis by P. W. Shimer of this unusual product gave: Si, 0.019; P, 0.228; S, 0,39; Mn, 0.042; C, 2.366; and graphite, 0:000 per cent. A cast of iron made just before the disturbance contained P, 0.98, and Mn, 1 per cent. The peculiar product seems to have been decarburized in the hearth and, at the same time, to have lost much phosphorus and manganese, either by the action of the blast in the empty hearth, or, more probably, by. contact with the cinder rich in iron which was formed at the time. Unfortunately, no specimen of the cinder was preserved, so its composition cannot be given. It seems very remarkable that, with the furnace in bad condition, the temperature should be high enough to keep such

Sep 1, 1908

By L. W. WALLACE

IN an engineering fashion we have made an assay of the engineering profession, using as a. sample the engineers listed in "Who&apos;s Who in America" (1928-1929). We are aware that some will say it is an unfair sample; that it came from the best mine. This is readily admitted, with this qualification: that all engineers and architects by virtue of their training and experience have been freed of most of the dross to which mankind is heir. They are -a selected group to begin with, having all the potentialities those in the sample possess. We are also aware that some will say a part of those included in the sample are not engineers. Our answer to that criticism is this: An engineer is no less an engineer because for the time being he is president of a bank, a university, an opera company, or a hotel company. Moreover, he is no less an engineer because he is a governor of a commonwealth, a United States senator, a member of the Cabinet, or the President of the United States.

Jan 1, 1929

By C. S. Sivaramakrishnan, Manjit Singh, Rajendra Kumar

Regarding liquid nzetals structurally as a suspm-sion of clusters , having derivated solid-state coordination, in truly liquid atoms, the recently developed Kuvlar-Samarin technique of centrifuging- in liquid state enabled the determination of the cluster sizes inAl-Cu mid Pb-Sn systems. It is shown that the colutne fraction of the clusters does not exceed 9 pct and the energy of their formation in Al-Cu is about 5.5 kcal per g-atom and in Pb-Sn eutectic alloys about 25 kcal per y-atoni. STRUCTURAL investigations of liquid state have principally followed the following three courses: i) studies with X-ray, electron, or neutron diffraction; these investigations have shown that there is a certain amount of regularity in the structure of liquid metals which can be defined by a coordination number and that the structure is a derived function of that in the solid state; ii) thermodynamical investigations which are based on the concept of ideal behavior; these describe the liquid state in terms of free-energy values and other thermodynamic functions; although these investigations are of help in the study of the general effects of alloying, they do not provide any structural insight into the precise atomic distribution in liquid state; iii) measurements of surface tension and viscosity; although it is natural to expect that the viscosity is related to the structure in liquid state, these investigations have so far only provided information which can be used by the foundry technologists and has been little utilized in formulating models of the structure of liquid state. As it happens, investigators in the three groups have worked almost independently of each other and there is practically no structural correlation between the results of one group with those of another. The purpose of the present paper is to indicate that the experimentally measured parameters of these three groups of research are closely related to the structure in the liquid state. STRUCTURE OF LIQUID METALS Although atomic distribution in solid and gaseous states is rigorously known, that of the liquid state is only appreciated on the fringes. There is no universal model of atomic distribution in liquid state, but two diverse models are at present hotly contested. The first, largely expounded by ~ildebrand,&apos; regards the liquids as condensed gas since many of their properties and much of their behavior can be adequately described by regarding them as fluids. The second mode12j3 considers that some form of near-solid as- sociation of large number of atoms exists in the liquid state. On the other hand, ~ernal&apos; was able to predict rather precisely the radial distribution functions in liquids on the basis of statistical geometric approach which considered that liquids are "homogeneous, coherent, and essentially irregular assemblage of molecules containing no crystalline regions or holes large enough to admit another molecule". He introduced the concept of pseudonuclei in the otherwise random structure as aggregates of closely packed tetrahedra which gradually merge into irregularity and continually replace each other. To what extent the pseudonuclei can be regarded as regions of near-solid association is indefinite but Bernal suggested that the concept of pseudonuclei can be compromised with the latter model if the near-solid associations are regarded as extremely dense and not necessarily crystalline. The difficulty in projecting the structure of liquid metals arises because they exhibit duplicity of character as some of their properties are closer to those of crystalline solids and others to fluids. There is an increasing tendency to discuss the structure of liquid metals in terms of the second concept according to which the structure of liquid metals may be conceived as consisting of i) clusters of atoms where the aggregation is a close derivative of that in the crystalline state, ii) individual atoms which behave like true liquids in respect to degrees of freedom and iii) excess number of vacancies. It is noteworthy that the introduction of only 5 pct vacancies is sufficient to transform crystalline matter into the liquid state. At any instant of time thermodynamic equilibrium exists between i, ii, and iii, but the relative proportion of the clusters and random atoms is not known. That this is so can be appreciated by the fact that, when liquid metal is rapidly cooled, liquid state vacancies may condense in the form of dislocation loops and vacancies in excess of their equilibrium number in solid state. These dislocation loops have been observed in thin foils of aluminum prepared from rapid cooled aluminum. As temperature increases above melting point the number and volume fraction of clusters decrease but those of vacancies and random atoms increase. Clusters are transient in nature. In pure metals the cluster is an aggregation of the metal itself. In alloys, however, the nature of the cluster largely depends on the interaction between solvent and solute atoms. If the interaction between unlike atoms is greater than between like atoms: the clusters are then aggregates of unlike atoms. Examples of this kind of system are A1-Cu, Mg-Pb, and so forth, i.e., systems which exhibit negative departures from the Raoult&apos;s law. In systems where the interaction between unlike atoms is smaller than be-

Jan 1, 1968

By B. D. Crawford, S. A. Falconer

ONE of the outstanding achievements in connection with this country&apos;s war efforts has been the ability of our mining industry to supply from domestic sources many of the minerals of strategic importance that formerly were obtained principally from abroad. In order to meet the war-born demands for these scarce minerals, it has frequently been necessary to develop special methods for treating ores and waste products hitherto considered too low-grade to be workable; and to improve the efficiency of older beneficiation processes. Important in this respect have been the recent technological advances in the field of froth flotation of nonsulphide minerals. Because of the refractory nature of many of these domestic ores, and, in many cases, the limited available technical data regarding their treatment, much research work has been necessary. The following examples describe the procedures and reagents used, and the results obtained, in certain laboratory flotation investigations conducted by American Cyanamid Company&apos;s engineers at the Cyanamid Ore Dressing Laboratory on ores containing such minerals as scheelite, manganese oxides and carbonate, ilmenite, brookite, kyanite, garnet, spodumene, mica, feldspar, celestite, fluorite, chromite, corundum, and cassiterite. In presenting these data, we wish to point out that many of the minerals listed have previously been tested, and their amenability to flotation reported, by other investigators-notably those of the United States Bureau of Mines. In some instances the procedures and reagents used in the treatment of some of the following described ores follow rather well-established lines, and with one or two exceptions, the reagents used were well known. However, many of the ores tested did not respond well to simple conventional procedures and it was necessary to adopt special methods of conditioning and desliming, reversal of the usual order of floatability of some of the minerals, multiple cleaning, etc., in order to secure separations. Except where otherwise noted, all numbered and trade-marked reagents mentioned in this paper are marketed by the American Cyanamid Co. or the American Cyanamid and Chemical Corporation. TUNGSTEN ORES Tungsten minerals, vitally important in the war industries of the United States, rank high in the list of those we formerly had to import in order to supply our needs. Most of our domestic ores of tungsten contain scheelite as the valuable mineral. Today there are in the neighborhood of twelve tungsten operations in this country where flotation is used as the main or accessory form of benefication. It has, of course, been known for some time that scheelite and other tungsten minerals respond to treatment by flotation.

Jan 1, 1944