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By William I. Watson

Problems encountered in beneficiating mineral raw materials become increasingly difficult as there is a shift to lower grade and more complex raw materials, and because of the economic need to strive for ever higher recoveries, higher grade products, and lower processing costs. Methods of attacking the many problems should include not only the familiar chemical and physical tests and equipment, but such techniques as X-ray analysis, infra-red analysis, differential thermal analysis, and the use of electron and X-ray microscopes. Many people in the mineral-treating field are unfamiliar with these newer methods and techniques. The differential thermal analysis method, in particular, does not seem to be very well known, even though it offers interesting possibilities in the study of many ore treatment problems.

Jan 7, 1959

By A. T. Robinson, J. E. Dorn

The electrical resistivities of aluminum alloys containing CU, Ge, Zn, Ag, Cd, and Mg were found to increase linearly with the atomic percentage of the solute atoms. Application of Linde's rule to these data suggests that each aluminum atom contributes 2.5 electrons to the metallic bond. ALTHOUGH aluminum invariably exhibits a Jt\. valence of three in ionic solids, it does not follow necessarily that its valence in the metallic state is also three. As a matter of record, many properties suggest that the number of bonding electrons in metallic aluminum is less than three. For example, as shown in Fig. 1, the atomic radii1 of the metallic elements in the solid state decrease with increasing atomic number at the beginning of any one period. The atomic radius of aluminum, however, is greater than that which would result from a regular decrease in atomic radius with increasing atomic number, suggesting that the number of bonding electrons in aluminum is somewhat less than three. Correlated with the anomalously large atomic radius of aluminum is its abnormally low melting temperature. As the atomic numbers increase in any one period, the melting temperatures of the metallic elements increase.' As shown in Fig. 2, however, the melting temperature of aluminum (13) is only slightly greater than that of magnesium (12). Again the number of bonding electrons in metallic aluminum appears to be nearer two than the expected value of three. In addition Ageev and Ageeva3 alculated the electron density distribution in the aluminum lattice. A comparison of such electron density curves for various assumed valence states of aluminum with experimentally determined curves suggests that the actual number of bonding electrons in metallic aluminum is between two and three. Hume-Rothery and Raynor', " have suggested that the above-mentioned abnormalities are associated with the overlapping of the Brillouin zones of metallic aluminum when it is in the usual face-centered cubic structure. The importance of the number of bonding electrons in metals has been extended recently into the field of mechanical properties. While formerly it was thought that the plastic properties of alpha solid solutions were primarily dependent upon the lattice strain induced in the solvent by the solute, it is now known that the difference in the number of bonding electrons of the solute and solvent also has its influence on the plastic properties."1' In order to achieve a satisfactory correlation of the effect of alloying elements on the plastic properties of aluminum alloys,"'T however, it was necessary to assume that the number of bonding electrons contributed by aluminum was about two rather than the expected value of three. It appeared to be desirable, therefore, to seek other criteria for evaluating the number of bonding electrons contributed by aluminum to its alpha solid solutions, especially in view of the practical as well as the theoretical importance of the effect of valency on the plastic properties. Norbury' was perhaps the first to illustrate that the increase in resistance of alpha solid solutions is associated with the differences in valence of the solute and solvent metals. In a series of illuminating investigations Linden-'' has shown that the electrical

Jan 1, 1952

By A. M. Gaudin, D. W. Fuerstenau

By streaming potential techniques, the zeta potential of quartz has been measured as a function of the concentration of dodecylammonium salts at different pH values. These experiments indicate that adsorption of dodecylammonium ions takes place as individual aminium ions until a certain critical concentration is reached in the double layer, at which point the adsorbed collector ions begin to associate into patches of ions, called hemimicelles. Because of its effect on the surface potential of quartz, pH controls the adsorption of dodecylummonium ions. The value of cooperating agents and nonionized constituents of flotation systems is discussed. Previous investigation of the role of pH in the flotation of quartz with anionic collectors is here extended to an inquiry of how the cationic collector, dodecylammonium acetate, is adsorbed at the quartz-solution interface. The equilibrium amount of this collector adsorbed by quartz has already been measured as a function of concentration and pH. The weight of prior evidence has suggested that two mechanisms are involved in the adsorption of this collector by quartz, but with existing adsorption measurements alone it is not

Oct 1, 1955

By R. J. Caro

The Anaconda phosphate plant was put into operation in the fall of 1923. Its present daily operating capacity is approximately 170 tons of treble superphosphate and 16 tons of phosphoric acid analyzing 42 pct P2 O5 and 52 pct P2 Os, respectively. As a result of the continued increased demand for phosphates, Anaconda decided in 1947 to expand the plant's daily output to 270 tons of treble superphosphate and 54 tons of phosphoric acid. The present daily plant intake is 335 tons of wet (footwall) phosphate rock analyzing 31.7 pct P² O5 and 0.28 pct V² O5. The rock is shipped from Anaconda's mine at Conda, Idaho, in open railroad cars, having been crushed to pass 3/8 in. mesh at the mine.' The expansion program will require an increased intake of 300 tons of rock per day. The hanging-wall rock anaIj-ses approximately 30.5 pct P2 O5 and 0.11 pct V² O5, and will be beneficiated in a new washing plant under construction

Jan 1, 1950

By B. D. Cullity

This investigation of bismuth-selenium alloys was made in an attempt to find a suitable material for use in thermoelectric generators. These devices are simply thermocouple circuits designed for the efficient production of electrical energy from thermal energy, which may in turn be derived directly from solar radiation or from the combustion of fuels. The requirements of a material for use in a thermoelectric generator are obviously quite different from those of a material used in a temperature-measuring thermocouple. Naturally, for power generating purposes, the thermoelectric power (voltage produced per degree difference in temperature between the junctions) must be as high as possible. Furthermore, in order to obtain reasonably high power outputs, the materials used in the generator must have an electrical conductivity which is as high as possible. Finally, in order to minimize heat lost by conduction to the cold junction, the thermal conductivity must be as low as possible. The relation between these several factors and the efficiency of conversion of thermal into electrical energy—the thermoelectric efficiency—has been discussed by Telkesl in a recent review of the subject. She gives the thermoelectric efficiency as: W o Efficiency = -Wo ______________i____________ TR-TC+ O2TR-Tc) where W, = power output in external load (watts) Wi = rate of heat input to hot junction (watts) TE,T, = temperature of hot and cold junctions (oA) K1,Kz = thermal conductivity of the two thermocouple materials (watts/cm°C) p,,pz = electrical resistivity of the two thermocouple materials (ohm cm) 9 = thermoelectric power (volts0/C) For many materials, some of the desired properties (for example, high electrical and low thermal conductivity) are almost mutually exclusive; the problem thus becomes one of finding a material which has the optimum combination of pfoperties. Bismuth-selenium Alloys work on the equilibrium diagram of the bismuth-selenium alloys has been reviewed by Hanson who gives the diagram reproduced in There are two intermediate phases in this system, BiSe and Bi²Se3. The existence of an alpha and beta modification of BiSe has not been demonstrated satisfactorily and the writer found no evidence of it in the present work. BiSe and Bi2Se3 have, like bismuth, a rhombohedra1 crystal

Jan 1, 1949

By Alfred Weiss

Daniel C. Jackling's innovative concept for handling low grade ores ushered in a new philosophy of open pit mining. As one of the greatest minemakers of all times he revolutionized major segments of the industry and helped strengthen US defense efforts during World Wars I and II by making possible the tremendous copper supplies from US mines. Many great mining men have since followed in his footsteps with their discoveries of new orebodies or development of new mines. Their brilliance in leadership can also be traced to the coupling of a new idea to the physical nature of the materials in the earth's crust or to the extractive stages of minerals recovery. The minerals industry is now in another era of change and must again devise techniques to meet the challenge. The task is not only to create new exploration techniques and develop new mining methods, but, I believe, to optimally apply new concepts and tools in daily decision-making.

Jan 11, 1978

By R. P. Rothwell

About thirty miles north of the city of Belleville (which is situated on a branch of Lake Ontario), and in the township of Marmora, Ontario, there is found a belt of gold-bearing quartz veins, which present geological mineralogical, and economic features of great interest to the profession. The district in which these veins are found is characterized as a rolling country, with low rounded hills of syenitic granite, overlain on the flanks of the hills by Silurian limestones, which lie in nearly horizontal beds, and in some places are so fine in texture as to afford lithographic stone of a fair quality. The gold-bearing veins run north and south through this belt of syenitic granite, and are quartz-filled true fissures, with micaceous or talcoid slates forming the walfs of and horses in the veins. This

Jan 1, 1881

By S. P. Rothwell

ABOUT thirty miles north of, the city of Belleville (which is situated on a branch of Lake Ontario), and in the township of Marmora, Ontario,: there is found a. belt of gold-bearing quartz veins, which present geological, mineralogical, and economic features of great interest to the profession. The district in which these veins are found is characterized as a rolling country, with low rounded bills of syenitic granite, overlain on the flanks of the hills by Silurian limestones, which lie in nearly horizontal beds, and in some places are so fine in texture as to afford lithographic stone of a fair quality. The gold-bearing veins run north and south through this belt of syenitic granite, and are quartz-filled true fissures, with micaccous or talcoid slates forming the walls of and horses in the veins. This

Jan 1, 1881

By Lawrence W. Teufel

An anelastic strain recovery technique is presented as a method of determining the directions and ratio of the maximum and minimum horizontal in-situ stresses from oriented cores from deep wells. Predictions of hydraulic fracture azimuth inferred from principal stress directions determined from both elastic and time-dependent (anelastic) strain relaxation measurements of volcanic tuff are consistent with the observed orientations of hydraulic fractures produced in simulation and mineback experiments, underground at the Nevada Test Site. In addition, anelastic strain recovery measurements on oriented cores of shale and sandstone from well depths of about 1680 meters show consistent relaxation directions of the principal horizontal strains and have enabled a prediction of the principal horizontal stress directions and hydraulic fracture azimuth.

Jan 1, 1982

By N. J. Grant, D. Carne, J. B. Seabrook

IT is unnecessary to review much of the literature on hydrogen embrittlement of steel since several excellent reviews and bibliographies exist.1-3 Hot acid pickling and cathodic charging have been known to cause hydrogen embrittlement of steel and have been used as laboratory methods to charge steels with hydrogen.4-8 Experimental Procedure The problem of prime concern in all instances, except in the work of Sims and coworkers,10 is that at no time was there a definite known hydrogen value reported which could be related to a particular value of the degree of embrittlement. It was the purpose of this research to determine the relationship between hydrogen content and degree of em-brittlement quantitatively. The 1020 stock used for the specimens was hot-rolled 7/16 in. diam rod of the following analysis: 0.19 pct C, 0.40 pct Mn, 0.012 pct P, 0.036 pct S' Vacuum-fusion analyses for nitrogen and oxygen gave 0.014 pct O2 and 0.0011 pct N2. Cathodic charging was used to cause embrittle-ment. The advantages of this method were that no quenching was necessary, the impregnation was reasonably controllable, and representative samples for analysis could be prepared simultaneously with the charging of the tensile bars. Analyses for hydrogen were made in a vacuum-fusion type of apparatus which extracted gas from the samples by fusion in a molten tin-iron bath' This apparatus, which has recently been described in detail elsewhere, will not be discussed here.". " Consecutive samples can be analyzed every 15 min with an accuracy of 0'03 ppm. A A from an electrolytic or pickling bath can be charged for analysis in about 3 min, and analysis completed in 15 min. Samples of as-received 1020 stock were analyzed and found to contain a negligible amount of hydrogen (0.06 ppm). Preliminary pickling and electrolytic charging gave highly variable results. Cold-worked samples showed higher values but ranged from 0.6 to 6.0 ppm of hydrogen. Charging at 90°C gave higher values of charged hydrogen, but troublesome films on many of the specimens resulted. It was not until a few drops of a catalytic poison, prepared from 2 g of yellow phosphorus dissolved in 40 ml of carbon disulphide,8 was added to the electrolytic cell that fairly consistent high values of hydrogen could be charged into the as-received 1020 steel at room temperature. The cell used is sketched in fig. 1. The anode and fixture for the tensile specimens were fastened to the cell cover as shown, and the specimen was screwed in place, centrally located with respect to the anode. At first, anodes of lead and graphite were tried, but they contaminated the electrolyte and gave a slight deposit on the specimen. Later, a platinum wire was used in the form of a uniform helix. A current of 2 amp, corresponding to about 0.5 amp per sq in. of cathode, was used for most specimens. The electrolyte was 4 pct H2SO4 solution. Fig. 1 shows the form of the special tensile bar, the main portion of which was an ordinary 1/4 in. diam, 1 in. gauge length test bar, except that two to four small cylinders of stock were left attached by small links to the bottom end of the tensile bar for the purpose of providing samples for hydrogen analysis. Thus the bars and samples were charged with hydrogen simultaneously and an analysis could be made while the bar was being tested mechanically. Experiments were performed to determine how representative the test cylinders were of the middle of the test bar proper. While the bar center was being analyzed, the small cylinder was stored in dry ice, since it had been shown that such storage prevents loss of hydrogen for many hours.12 The results of these checks are shown in table 1. The checks are very good (0.3 ppm) and indicate that it is permissible to use the small end cylinders to establish the hydrogen content of the tensile test bar proper-

Jan 1, 1951

By O. C. Wheeler

Peru, if it is judged on a basis of its annual production rate, can be ranked seventh among the oil-producing countries of the Western Hemisphere. In 1945, as in each of the three previous years, the country again produced about 14 million barrels of crude petroleum.

Jan 1, 1946

By Earl C. Willis

In selecting new or replacement mining machinery to be purchased, there are many considerations to be discussed and taken into account, the most important being the productivity of the machine and the maintenance cost and downtime to be expected with the new equipment. Productivity of a given mining machine is evaluated by the Industrial Engineering Department: analysis of potential upkeep and downtime calls for the Maintenance Department to enter into the task of evaluating new mining machines. This is a very important function of the maintenance department because a wrong decision or mistake in judgment, particularly in a commercial mining company, can be exceedingly expensive. Once the type and size of a machine is decided, an examination of units fitting the basic requirements will sometimes show one particular machine which has a distinct edge on the competitive machine. In this case, the decision is easy. However, in most cases, the performances of the machines being considered are so close that the decision becomes one that is very difficult to make on performance alone. Serious consideration must then be given to maintenance performances and features of the machine which would permit lower maintenance and less downtime.

Jan 7, 1963

By Craig R. Barrett

The influence of the stress dependence of the dislocation density on the overall stress dependence of The steady-state creep rate is discussed. Experimental measurements of dislocation densities and creep rates jor an Fe-3.1 pct Si alloy tested over a wide range of stress are presented which indicate a close correlation between the two quantities. EXPRESSING the stress dependence of high-temperature steady-state creep rates has been the subject of numerous investigations over the past decade. From these investigations have emerged a few general equations which fit most of the available data reasonably well. Garofalo 1 has proposed that for a wide range of stress and temperature the creep rate, i, can be expressed by a relationship of the form: where A, ß, and n are temperature-dependent and is the applied stress. Eq. [I] gives a stress dependence of a at low stresses and exp(nßo) at high stresses, both consistent with experimental observation where n = 5. A number of other investigatorshave proposed a similar expression where: where m and w are in general functions of temperature. Theoretical justification for Eqs. 111 and [2J comes from two different approaches, theories based on dislocation glide3-5 and theories based on the balance between work-hardening and recovery.' Dislocation glide theories predict where p is the mobile dislocation density and V is the activation volume. In order for Eq. [3] to predict a on stress dependence at low stresses with n = 5, it is necessary for p to be a strong function of stress, about proportional to u3 or u4.436 Recovery models of creep start with the general expression:' where r is the recovery rate and h is the work-hardening rate, and then employ a detailed model to determine the stress dependencies of r and h. As example, weertman2 has described a model based on pile-up hardening which results in an expression similar to Eq. [2] with m = 2 and p = 2.5. A recent, seemingly more general approach suggested by McLean is to use Friedels dislocation network growth expression to calculate the stress dependence of r. This model predicts r = p 3,2 and, as h is taken to be a relatively weak function of stress, the stress dependence of i should be about proportional to p3, 2. Once again, it is required that p be a strong function of stress to yield i This recovery model is by no means complete as the stress dependence of network growth is calculated in the absence of an applied stress meaning that r should probably be a stronger function of stress than given by p3, 2 and also some recent work by Mitra and McLean8 suggests that the stress dependence of h may be as large as Because of the importance of the stress dependence of p in determining the overall stress dependence of the strain rate it seems reasonable to examine this relationship in some detail. Measurements made on dislocation densities present during high-temperature steady-state creep generally obey the following relationship a =o0 + aGVWp [5] where uo is usually called a friction stress, a is a numerical constant about equal to unity, G is the shear modulus, and b is the Burgers vector. Depending on the magnitude of uo, data obeying Eq. [5] can give rise to a range of stress dependencies of p. For example, if we assume that the expression where 6 is some constant, adequately represents the stress dependence of p over a range of o, then from Although Eq. [6] obviously breaks down when u 5uo for uo 6 can vary over a wide range of values. In particular, if u > a, > 0 then 6 will be greater than 2. As an example the data of Ishida and McLean are plotted in Fig. 1 showing excellent agreement with dynes per sq cm) and also showing good agreement with a p cc u3 dependence when plotted on a log-log basis. As oo increases 6 tends to increase and correspondingly the stress dependence of the predicted creep rate should also increase,* as-

Jan 1, 1968

By L. F. Stutzman, George Thodos

The friction factor plot presented by Cornell and Katz4 and developed for the flow of fluids through consolidated formations has been directly adapted for handling fluid flow problems involvitrg both linear and radial flow. In this adaptation the friction factor plot is used directly for the solution of problems and thereby eliminates the use of conventional equations which are specific to laminar (Darcy) or turbutent flow. This upproach overcomes the disadvantages inherent in the use of these conventional equations. It eliminates the necessity of checking the type of flow occurring in order to identify the specific equation which must be used. In radial flow problems, because of the increasing mass velocity of the fluids as they approach the wellbore. the type of flow may no longer remain laminar. Consequently, it is necessary to use more than one equation in a problem and to identify the range over which each equation should be applied. Finally, in practice it has been found that much of the flow of gases through consolidated media occurs in a range that is neither laminar or turbulent. For this transitional region, no convenient equations are available. The method and presented friction factor plot are appficahle to both liquids and gases. INTRODUCTION The flow of fluids through unconsolidated media in packed beds has been treated extensively by a number of investigatorsl,2,3,5,7,8 Most of these studies present friction factors as a function of modified Reynolds number similar to those developed for conventional fluid flow through pipes. These friction factor plots are presented for linear flow; however, Elenbaas and Katz have extended these concepts to apply to radial flow. All of these studies on unconsolidated materials require a knowledge of packing properties such as sphericity. porosity, and particle diameter. Sphericity and particle diameter cannot be defined at the present time for consolidated formations such as those commonly found in gas or oil reservoirs. As a result many investigators have not utilized friction factors and Reynolds number in the study of fluid flow through consolidated media. However, Cornell and Katz4 present a plot (Fig. 1) for the flow of fluids through consolidated porous media, in which the friction factor defined as: The turbulence coefficient, P, is related to the formation permeability, K, as presented in Fig. 2. Three different types of flow may exist in the flow ot

Jan 1, 1957

By Robert R. Brookshire

Brush plating has been thought of by many as black magic bordering on alchemy. Actually it is a science that uses both electro-chemical and mechanical engineering skills and technology. We are not sure when brush plating was first used or by whom. I do know that many times when we would put in for patents on things we thought of as new and innovative, we would find that someone had done it many years before. It took World War I1 to get brush plating off and running. Now at this point, someone may be asking just what is brush plating? And why are we plating brushes? One way of describing what brush plating is, is by telling what it is not such as tankless plating. Brush plating-is an electro deposition of an electro-platable element or alloy onto a conductive surface. To do this a source of direct current is required; this can vary widely. I prefer stepless voltage control from 0-35 volts with a capacity depending on the size job to be done. This can vary up to 500 amps for normal applications. In one case we have used 7500 amps.. In the beginning a brush was actually used with a wire in the middle of the bristles and a jelly-like paste made up from tank plating solutions. The bristles were saturated with the gunk and the spot to be plated was muddled with the concoction at a potential which was the same as the applied tank Voltage. Metal was deposited but only thin coats were achieved. Today we use graphite wrapped or covered with cotton to form a Q-tip type anode. By using graphite rather than a specific metal we are able to either plate, de-plate or strip, electro- mill, electropolish, or anodize--all with the same equipment. Only the electrolyte needs to be changed.

Jan 1, 1984

By Paul L. Cloke, S. R. Titley

Paul L. Cloke (Assistant Professor, Dept. of Geology and Mineralogy, The University of Michigan, Ann Arbor, Mich.) - On examination of the paper by S. R. Titley it appears that several errors have been made, many of them of a fundamental nature. It is the intent of this discussion to point out these mistakes, and, insofar as possible with the data at hand, to correct them. EXPERIMENTAL WORK Ferrimolybdite-Limonite-Water: The results of the experiments described are very difficult to interpret; nevertheless, a correct interpretation is essential as is pointed out subsequently. The difficulties become apparent when reasons are sought for the continuing change of pH after conversion of ferrimolybdite to ferric hydroxide and for the change of pH when -stirring is stopped after a steady value has been reached. In seeking an explanation of this experiment it seemed to this writer that the (temporarily) steady pH values might be due to kinetic rather than equilibrium effects. In this view the steady pH on stirring might be explained as a balance of several reactions proceeding simultaneously. The first of these would be the slow solution of ferrimolybdite,

Jan 1, 1964

By John V. Beall

Since the U. S. Metals Refining Co. works was established, around the turn of the century, near the town which is now called Carteret, N. J., it has grown to be a major producer of refined copper and the main source of that special brand known as "oxygen-free high-conductivity copper." Owing to the complex metallurgical problems arising from handling a variety of raw materials such as copper concentrate from Matahambre, Cuba, copper and brass scrap from the New York area, and domestic blister copper, the organization is geared from top management down through its 2000 employes to maintain a high degree of flexibility in plant operation. The Company is a subsidiary of The American Metal Co. Charges for the smelter furnaces, one reverberatory furnace and one blast furnace, are made up in. bedding bins so that they may be tailored to the production of a constant grade of blister copper. The reverberatory furnace smelts the .sulphide charge, which may be a blend of ten different materials but principally the Cuban concentrate, and the matte from the process is poured into a converter. This reverberatory is 80 by 20 ft, silica lined with a slag bottom, fired by pulverized coal, and continuously side-charged from the top by bottom-dump cars which keep the side walls covered. It produces a 40 to 50 per cent copper matte. The fuel-charge ratio is 4.35 tons of solid charge per ton of coal. The furnace has a capacity of 10,000 tons of charge per month and produces from 5000 to 6000 tons of slag per month which must be disposed of. About 5000 tons of converter slag is produced monthly and returned molten to the reverberatory furnace. The converter gases go through a spray chamber to a Cottrell precipitator and thence to the flue system. Smoke from the

Jan 1, 1948

By Robert W. Bartlett

A computer model for predicting the rate of oxidative leaching of copper from fragmented low grade sulfide ores is presented. The model involves the kinetics of the dissolution of chalcopyrite grains and solution diffusion of oxygen within rock pores. Adjustable curve fitting parameters are not used. The model was tested by comparing computed extraction curves with experimental results for a -11 inch ore obtained by block caving and leached at 90°C and 400 psi oxygen for one year at the Lawrence Livermore Laboratories.

Jan 1, 1973

By R. W. Parsons

wben a displacement front encounters an isolated permeability heterogeneity, it will be perturbed. The details of this perturbation will depend on the beterogeneity size and shape, the Permeability contrast, and the mobility ratio. This paper deals with the displacement front behavior for one, simple, mathematically tractable model: a circular permeability discontinuity and unit mobility ratio. The progress of an initially planar front is shown for four permeability contrasts: k2/k1 = 0, 5/2, 2, m. The front distortion is more pronounced than streamline and isopotential distortion and it approaches a constant shape downstream from the discontinuity. INTRODUCTION The impact of reservoir heterogeneities on oil displacing processes depends upon the variation of the heterogeneous property (frequency distribution), its disposition (spatial distribution), and the inherent stability of the displacement mechanism.l The interplay of these factors plus the impracticability, if not impossibility, of describing a natural rock system in any detail makes exact displacement front movements difficult to determine. It is useful, however, to be able to qualitatively visualize what heterogeneities will do to a displacement front. In this respect certain simple models that can be treated analytically are of value. The following analysis will show the displacement front behavior for one such model. MODEL DESCRIPTION The flow field is two-dimensional and infinite in extent. The fluid flow is single phase, steady state and unidirectional at x, y = 2 m, or before insertion of the discontinuity. A circular permea- bility discontinuity is placed at the origin. Porosity and thickness are the same within and exterior to the heterogeneity. This is exactly the same model that was used by Greenkorn et al. to check analytically Streamlines as determined by Heie-Shaw flow models and finite difference computer techniques.2 FRONT POSITION CALCULATIONS The results of displacement front calculations are presented in Figs. 1 through 4 for four different permeability contrasts: k2/kl = O, %, 2, m. The times corresponding to the front locations are the Same for the 0 and cases! and for the 1/2 and 2 cases. The determination of front positions at various times is based on known analytical expressions for velocity potentials ().2 and stream functions ().2 These expressions are in terms of the x and y

Jan 1, 1969

By Henry A. Wriedt, John Chipman

Equilibrium in the reaction of hydrogen gas with oxygen in liquid nickel, iron, and their alloys has been studied at temperatures of 1500° to 1700°C. The equilibrium con^stant, 0/p, [% O], is greater in nickel then in iron by a factor of 45 at 1594 C. In the alloy steel range, the activity coefficient of oxygen is slightly increased by the presence of nickel. NICKEL is more resistant to oxidation than is iron, in both the solid and the liquid state. The solubility of oxygen,' however, is greater in nickel than in iron. The two metals and their liquid alloys constitute an interesting series of solvents in which the chemical behavior of oxygen can be studied by methods similar to those used for liquid iron.' Experimental Method The furnace assembly, including the tube for preheating the entrant gas, was the same as that described by Gokcen and Chipman. " controlled mixture of water vapor, hydrogen, and argon preheated to approximately the melt temperature impinged upon the surface of the liquid metal. The charge, weighing about 35 g, was held in an alumina crucible at constant temperature in the gas stream for a prolonged period, then quenched in a stream of cold helium, sampled, and analyzed for oxygen by the vacuum fusion method. The temperature of the liquid metal was measured by a Leeds and Northrup optical pyrometer which had been checked against a similar instrument certified by the National Bureau of Standards. The freezing point of electrolytic iron in hydrogen, taken as 153j°C, was used for frequent checks. This point and the emissivity determined by Dastur and Gokcen" established the transmissivity of the optical system. The emissivities of Fe-Ni alloys at 1535" are known from the experiments of Smith and Chipman,h nd it was assumed that the variation with temperature is parallel with that of iron. Recorded temperatures are probably accurate within k5"C. Preparation of Gas Mixtures—Since the ratio H,O:H, had to be much higher for nickel than for iron, it was found convenient to construct two separate systems for gas preparation. In both cases, the ratio of argon to the sum of the other two gases was at least 4, the proportion of hydrogen and water vapor being varied to produce H,O:H, ratios from 0.2 to 70. The primary purpose of the argon was to diminish the errors caused by thermal separation' in the gas phase. In addition, its presence lowered the saturation temperature required for a given H,O:H, ratio and minimized the difficulty of preventing condensation. Both systems were modifications of the one used by Dastur and Chipman.' For H,O:HI ratios greater than 2, welding-grade argon purified by passage over magnesium chips at 620°C was mixed with hydrogen produced in the electrolytic cell shown in Fig. 1. The design was based on a cell used by Bodenstein and Pohl," the important features of which area nickel wire cathode and sodium hydroxide solution as the electrolyte. The rate of hydrogen evolution was controlled by a calibrated ammeter and a rheostat in the circuit, the current efficiency being taken as 100 pct. Precise control of the argon flow rate at about 300 ml per min was achieved by means of a capillary flowmeter having a controlled pressure drop. The molar flow rate was measured volumetrically before each run, and a constant flowmeter setting was maintained thereafter. The A-H, mixture passed through a water saturator of the type previously described," the saturation temperature being maintained automatically with a fluctuation of k0.04"C. The tube between saturator and furnace was heated by a resistance winding. The system was of all Pyrex construction with the exception of the stainless steel tube containing magnesium chips. This was connected with the glass tubing at the upstream end by

Jan 1, 1957