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By R. L. Pober, L. Kaufman, E. V. Clougherty

Composite structure of hafnium, zirconium, and titanium diboride with additions of metals and/or compound phases were prepared by reactive high-pressure hot pvessing and evaluated in air and in mixtures of oxygen and helium at temperatures up to 2400°K and at linear flow rates of 0.1 to 0.2 ft per sec stp. Oxidation characteristics, principally depth of conversion of diboride to dioxide, were determined by a gas analysis method and by postoxidation metallo-graphic analyses. The best oxidation resistance was observed for hafnium diboride-silicon carbide composite which exhibited a 6-mil conversion to dioxide for a 1-hv oxidation in air at 2200°K compared to a 20-mil recession for hafnium diboride with no additive. Analogous improvements in oxidation resistance were observed for the addition of silicon carbide to zirconium. EARLIER investigationof the oxidation behavior of the diborides of the transition elements of Groups IVA and VA in flowing gas mixtures have produced a ranking of these compounds according to which HfB2 is the most oxidation-resistant followed in turn by ZrB2 > TiB2 > TaBz > NbB2. Other ~tudies~-~ have examined the physical, thermal, and thermodynamic properties of these diborides to provide a sound basis for the more detailed and specialized investigations which are required to generate the information needed to assess the usefulness of such materials in high-temperature oxidizing environments. Recent oxidation studies7 have examined the effect of variations of metal and boron content on the oxidation characteristics of zirconium and hafnium diboride in flowing gas mixtures including air and helium plus oxygen. Results obtained in the latter investigation confirmed the superior oxidation resistance of HfB2 over ZrB2. Moreover, metal-rich compositions of hafnium diboride showed improved oxidation resistance over boron-rich compositions at temperatures up to 2000°K; at higher temperatures the differences are not distinguishable. In particular HfBI.7 exhibited a diboride to dioxide conversion depth of 4 mils in 1 hr at 2000°K; HfB2. 2 exhibited a conversion depth of 16 mils for the same exposure.~ Specimens for the study of metal and boron stoichiometry on the oxidation characteristics of HfB2 and ZrB2 were prepared by high-pressure hot pressing, a specialized type of fabrication which produced dense crack-free bodies of the desired compositions with no significant impurity introductions. The purpose of the present investigation was to explore the possibility of further improving the oxidation resistance of the metal-rich ZrB, and HfB2. The plan to accomplish this objective was based in the formulation of several diboride compositions containing other compounds and phases which are generally known to have good oxidation resistance in one or more types of test environment. Ideally, such additives would also enhance or at least not diminish other boride property values principally mechanical strength and those parameters related to thermal stress resistance. The additions selected for HfBz included zirconium, aluminum, and (Ta + TaB2) designed to produce ternary metal diborides, hafnium to form a discrete HfB phase, chromium to provide a metal skeletal phase, (Hf + Si) to form a discrete hafnium silicide phase, and Sic to provide a discrete second phase. Additions to ZrB2 included A1 + B designed to produce a ternary metal diboride, Zr + Si to form a discrete zirconium silicide phase, and Sic to provide a discrete second phase. All the specimens were prepared by high-pressure hot pressing which was used to advantage to fabricate billets of the variety of compositions desired and suitable for oxidation testing. The present investigation also included the evaluation of high-pressure hot-pressed TiB2and TiB2-20 vol pct Sic, conventionally hot-pressed Boride 2,' and KT silicon carbide. Boride

Jan 1, 1969

By John J. Porter

UNUSUAL problems have arisen at certain iron blast-furnaces in Virginia through the fact that the ore-supplies, derived from the Oriskany formation, contain from a trace up to 1 per cent. of zinc oxide. Since the technical literature bearing on this subject is very scant, the following notes, based on personal experience, will probably be of value to those of our members who are interested in iron blast-furnace practice. The course of zinc through the blast furnace is readily traced. Entering the throat as zinc oxide, finely disseminated through the ore, it descends unchanged to the fusion-zone, since a temperature of 1,000° C. or more is required for its reduction. At the fusion-zone, the zinc oxide is reduced by solid carbon to metallic zinc, which is set free as vapor and rises with the ascending gases to the cooler zones of the furnace. In cooling through the range of temperature from 1,000° to 500° C. the zinc is re-oxidized according to the reaction Zn + CO2 = ZnO + CO, and the resulting zinc oxide, being in a very fine state of division, is readily carried along by the ascending gases. Portions, however, deposit on the descending stock and are carried down, again to pass through the same cycle of changes. Still other portions deposit on the lining of the stack, and gradually form hard masses of "cadmia." Of the remainder of the zinc oxide, the greater part passes out of the furnace, and is either deposited in the down-comer, dust-trap, stoves, boilers and flues, or passes through the chimney into the atmosphere. A small portion escapes reduction and enters the slag as zinc oxide, while still another portion is absorbed into the lining of the furnace.

Sep 1, 1907

By M. P. Tixier, A. Poupon, M. E. Loy

Simple qualitative methods are explained for identifying those shaly sands in a well that are most likely to contain oil. A need for more precise measurement of the variables that enter shaly sand analysis is indicated. Field examples are given to illustrate the methods. A theoretical discussion of the quantitative interpretation of shaly sands is given as a basis for discussion and as a guide for the future. While not generally capable of practical application at the present time because of the lack of sufficient accuracy of the electric log data, these methods may become more feasible in the future as the result of the improved logging methods now being introduced. INTRODUCTION Experience has shown that for porous formations containing only a negligible amount of clayey material, reliable information on the fluid saturation and porosity of the reservoir rocks can usually be derived from the electrical logs. The interpretation is based on empirical formulae relating the true resistivity of a porous formation to its lithologic character, to the resistivity of the interstitial water, and to the proportions of water and hydrocarbons in the pores.' If the resistivity of the interstitial water is not known, its approximate value can be derived from the SP curve.2,3 The porosity can usually be determined to a good approximation from a MicroLog, or a MicroLaterolog.4,5 When the reservoir rocks contain an appreciable percentage of clayey material, an additional factor is introduced into the analysis. In a clean formation, the matrix is an electrical insulator, so that the ability of the formation to conduct current is due only to the conductivity of the electrolytes in the pores; in a shaly formation, the shale constitutes a part of the rock matrix able to conduct current, and influences the resistivity of the formation. On the other hand, the spontaneous emf's and the circulation of the SP currents are also responsive to the presence of the shaly material. All other factors being the same, the deflection of the SP curve opposite a shaly permeable formation is smaller than the deflection which would be observed if the formation were clean. The effects of the presence of shale on the resistivity and on the SP curves in a shaly formation are functions of the amount, of the specific resistivity, and of the geometrical distribution of the shaly material within the formation. The presence of shale therefore constitutes an important complication in electrical log interpretation. It is easy to realize, for example, that the presence of a large amount of clayey material in a sand may have such a predominant effect that the resistivity of the sand will not change very much, whether the pores are entirely filled with connate water, or contain a high saturation of hydrocarbons. Important research projects have been undertaken to investigate the influence of shales and to find a way to allow for this influence in the interpretation of a log. The problem of the SP in shaly sands was analyzed mathematically by H. G. Doll"' for the case of sands with shale laminations. Formulae expressing the resistivity of shaly formations were proposed by Patnode and Wyllie8 and de Witte.9 Other quite interesting theoretical and experimental results have been published by various authors.l0,ll,12,l3,14 The purpose of the present paper is to discuss an approach to electrical log interpretation in shaly sands. This approach is based partly on some of the theoretical and experimental data available in the literature and partly on observations made on actual field logs. Comparatively simple methods for qualitative and semi-quantitative analysis are described. These methods depend principally upon information provided by the electrical logs.

Jan 1, 1955

By G. W. Form, W. A. Spitzig

The effects of hydrogen and vacuum shtering treatments on the physical and mechanical properties of arc plasma-sprayed tungsten were inuestigated. Temperatures examined ranged from 3000" to 4000°F in vacuum and 2000" to 3000°F in hydrogen for both single and duplex sintering cycles. Densities of 92 pct of theoretical density were obtained when a long-time hydrogen treatment at 2000°Fpreceded sintering in vacuum at 4000°F for 4 hr. This cycle also produced the highest ualues for modulus of rupture and bend angle. The results of this investigation point out the desirability of using a low-temperature long-time hydrogen treatment prior to a high-temperature vacuum sinter for arc plasma-sprayed tungsten. ADVANCES in the development of arc plasma-generating equipment have provided a high-temperature heat source that makes the fabrication of tungsten shapes possible by a metallizing process. Tungsten in the as-sprayed condition is very brittle. It has a density between 80 and 85 pct of theoretical density, a lamellar structure with elongated pores, and a high interstitial impurity content. To improve these properties, sintering treatments can be applied to the as-sprayed material, similar to those used for the densification of compacted tungsten powder. However, in view of the differences in the density and microstructure of as-sprayed tungsten as compared with compacted tungsten, responses to sintering were expected to be different. EXPERIMENTAL PROCEDURES The tungsten powder used in this investigation had a particle size varying from 3 to 13 p with an average diameter of 8p. The impurity level was less than 0.1 pct. The arc plasma spraying was done with an F-40 Thermal Dynamics Corp. plasma jet. Spraying was performed in air and thus required cooling of the substrate by an air blast in order to minimize oxidation. The spraying parameters employed in the fabrication of all specimens are listed below: Power input, kw 12 Arc-gas flow, cfh 95N2 + 5H2 Powder feed rate, g per min 33 Powder carrier gas flow, cfh ION, Spray distance, in. 3 Traverse rate, in. per min 30 Mandrel speed, rpm 100 Nozzle orifice, in. 7/32 These values of the spraying parameters correspond to optimum conditions ascertained in a previous study. Sintering was conducted at 3000°, 3500, and 4000°F in vacuum (< 0.1 Hg), and at 2000 and 3000°F in hydrogen. Duplex sintering treatments investigated are listed in Table I together with the designations that will be used for reference throughout this paper. The samples were fabricated by spraying onto a copper mandrel which was removed prior to sintering. The specimens used for the sintering analyses had the shape of small hollow truncated cones 1 in. high with an inside diameter varying from 0.500 to 0.125 in. and a wall thickness of 1/8 in. Specimens for bend testing were taken from hollow hexagonal prisms 1-1/2 in. high with a 1-in. diam across the flats and a wall thickness of 1/8 in. The bend-test specimens were ground to the dimensions 0.085 by 0.350 by 1-1/2 in. Prior to bend testing 0.0025 in. of stock was removed from each surface by electro-polishing. Density measurements were made by the water-displacement method. In addition, a porosimeter was used to determine the amount of interconnected porosity for representative samples. Strength and ductility were determined from recorded values in transverse bending using a cross head speed of 0.020 in. per min. The load was applied at the midpoint of a 1-in. span. The deflection data reported herein refer only to the plastic portion of the total deflection. RESULTS AND DISCUSSION The as-sprayed samples had a density corresponding to 83 pct (l pct) of the theoretical density of tungsten. Fig. 1 shows a representative as-sprayed tungsten structure.

Jan 1, 1964

By H. D. Outmans

The mechanics of filtration are described by a theoretical-empirical nonlinear diffusion equation which, under certain circumstances, may,be linearized and then solved explicitly. For filtration under static conditions linearization leads to a boundary value problem analogous to a heat flow problem with a known explicit solution. The corresponding solution for static filtration is compared with published experimental data. Under dynamic conditions filtration takes place in three successive stages. During each of these the rate of filtration and/or the thickness of the filter cake are different functions of the filtration time. The proposed mechanism explains the observed high resistance of dynamically deposited filter cakes against erosion and also the connection between filtration rate and viscosity of the drilling fluid. Several of the quantities governing dynamic filtration have no counterpart in the static filtration mechanism. The static filtration rate is, therefore, not a reliable measure for the dynamic rate and vice versa. INTRODUCTION Filtration under simulated borehole conditions, i.e.. either from a static suspension or from a suspension flowing parallel to the filter cake (dynamic filtration), has been the subject of several laboratory studies.1-7 This experimental and theoretical work showed that many aspects of the filtration mechanism cannot be explained by an elementary filtration theory based on the assumption that the filter cake is incompressible. For a more satisfactory theory compressibility should be taken into account. This has been done. at least to some extent, in the filtration theory developed for the chemical industry. Surveying the literature (see Ref. 8 for a bibliography) it becomes apparent that, although several properties of filter cakes deposited from many different suspensions have been measured, including compressibility, the filtration equations are essentially empirical in nature. No attempt has been made, for instance, to develop filtration theory along the lines of consolidation theory.12 This theory, upon which a highly successful development in soil mechanics rests, would appear to be an excellent starting point for a filtration theory since the compressibility concept is an essential part of it. As we will use this theory in the following development it is well to state the four assumptions on which it is based: 1. The fluid flow through a compressible porous medium is governed by Darcy&apos;s law. 2. The rate of change in fluid content of an element of the porous medium is proportional to the rate of change of solid pressure between the particles. 3. The solid particles are incompressible within the range of pressures considered. 4. The total pressure on a surface normal to the line of flow is equal to the sum of the fluid pressure and the pressure between the particles (solid pressure) at that surface. To calculate the rate of filtration and other quantities of interest it is necessary to know the filter cake compressibility and the permeability as a function of the solid pressure. It has not been possible to calculate these functions from theoretical considerations and they will therefore be introduced in this paper as empirical expressions. Both are determined in a compression cell where the cake is subjected to a mechanical load. Permeability and compressibility are measured after the solid pressure has stabilized, i.e., after the excess fluid pressure has been dissipated and the uniform pressure is transmitted entirely by the solids. The permeability and compressibility thus determined are not the same as during filtration in the borehole, under either static or dynamic conditions, because then, due to frictional drag, the solid pressure and hence also the permeability and compressibility vary along a line normal to the direction of the mean flow and can only be defined locally. DERIVATION OF THE FILTRATION EQUATION FOR COMPRESSIBLE FILTER CAKES As the filter cake in the borehole is thin compared to the radius of the hole the filtration may be considered as linear. Taking the x-axis normal to the wall, with its origin at the formation, we have, according to Darcy&apos;s law,

By E. Topanelian

In recent years considerable progress has been made in the development and application of mathematical techniques for the solution of certain problems involving economic "strategies". Such a problem might involve, for example, the scheduling of shipments of a commodity from a number of sources to a number of destinations. The object would be to schedule the shipments in a manner so as to satisfy the destination requirements and at the same time minimize the transportation costs. The solution to such a problem is not necessarily intuitively obvious. The "obvious" solution is frequently far from optimum. If the shipments are to be made from, for example, only two sources to four destinations, the optimum schedule is readily found. However, if shipments are to be made from, say, 10 sources to several hundred destinations, even a competent and experienced scheduler may spend considerable time in finding a reasonable answer. Even then he is not sure that he has the optimum solution. Furthermore, he has no way of knowing how far from optimum the answer is. Consequently, he does not know whether he should accept this solution or seek a better one. Prior to the advent of large high-speed digital computers, little more could be done with such problems because of their great size and multiplicity of possible solutions. A problem involving 20 sources and 50 destinations would require choosing, from a very large number of possible combinations, the optimum combination of 1,000 variables. The best one could do was to utilize intuition, extrapolation from past experience, and other non-exact approaches. With a high-speed computer, however, such problems can be solved providing a reasonable computational procedure (or algorithm) can be utilized. The purpose of this paper is to describe such a procedure (linear programming) and to apply this procedure to a production scheduling problem. THE RESERVOIR PROBLEM A simple reservoir model is used throughout this analysis to illustrate the use of linear programming. Even the simplest reservoir behavior problem is nonlinear in both space and time, but if the geometry is fixed for a particular study and the time variable is quantized, the resultant system may be described by linear constraints on the variable production rates. Crude oil is available from five separate sources and is delivered to a pipeline. Sources 1, 2, 3 and 4 are ideal reservoirs and therefore are subjected to reservoir flow restrictions. Source 5 is labeled "Outside Source" and crude oil from this source is assumed to be available in unlimited quantities without considering reservoir conditions. The general problem is to determine the schedule of crude oil production from five sources which, over an eight-year period and subject to certain restrictions, will result in maximum profit. "Profit" is defined to encompass all economic factors and expenses involved in producing and selling crude oil to a pipeline facility. Such economic factors are lumped to the extent that the term represents the dollars profit from one barrel of crude oil from any of the five sources entering the pipeline system. Table 1 presents the assumed profit per barrel for oil from any of the five sources over each of the four time periods. In this chart the eight years is broken into four equal intervals of two years. The selection of four time periods of two years each and the values representing the potential profit are completely arbitrary selections for the purpose of illustrating this idealized reservoir problem. In any practical application of this work a careful economic study would have to be made in order to estimate potential unit profits for time periods as far in the future as eight years. In this particular study it is assumed that all of the potential unit profits (C) are known and fixed before the production schedule is attempted. For each reservoir arbitrary values are assigned for

By S. T. Yuster

An analysis has been made of the factors responsible for tilted fluid contacts in petroleum reservoirs. The factors are static and dynamic with the former being controlled by those variables responsible for the capillary rise of fluids, and the latter include rate of formation tilt and hydraulic circulation. The explanation that rate of formation tilt may be responsible for tilted contacts appears untenable. The role of some of these factors in the migration, fractionation. accumulation and possibly the prospecting for oil is indicated. INTRODUCTION While it is generally considered that the segregation of gas, oil, and water in a petroleum reservoir results in approximately horizontal planes separating these phases. there are factor; which modify this simplified picture to a very great extent. Some of these factors are static. and the departure of the fluid interfaces from horizontal may represent a static equlibriun. Some of these factors may be dynamic and the interface positions may be non-equilibrium and represent a steady .state condition. Of course combinations of these two situations may also exist. The reasons most commonly given for this behavior are hydraulic circulation of fluids, change in character of the formation, and a rate of tilt of the formations more rapid than the rate at which the fluids may re-establish an equilibrium. Russell&apos;s Principles of Petroleum Geology&apos; contains an extensive discussion of tilted fluid interfaces and their importance in the migration and accumulation of petroleum. Russell cites examples of tilted water tables at Lance Creek, Wyo.; Rock River, Wyo.: Cut Bank. Mont.; Cushing, Okla.: and Graham; Okla. Also given was the Wasson Field of West Texas which has saucer shaped oil-water and gas-oil interfaces with the saucer being deeper in the case of the oil-water contact. The Bradford Field in Pennsylvania has a tilted water table. San Ardo. Coalinga None and some other California field.; have tilled contacts. A recent paper by King Hubbert discuses the effect of hydraulic circulation of the water underlying the oil in a given stratun and it- implications in the accumulation of and drilling for the oil. The foregoing would indicate that tilted fluid interfaces are not uncommon and that it would be of importance to underbtand the forces which are responsible. Further. it would be of interest to examine certain idealized models of situations which may cause tilting with the thought in mind of deriving relatinnships between the important variables. These relationships may only hold exactly for the model* assumed but the results may apply semi-quantitatively to actual formations and at least indicate trends. The discussion will be divided into the effect of static factors and the effect of dynamic factors. STATIC FACTORS It has already been mentioned that one reason given for tilted contacts is a variation in formation properties. Specifically this is a change in the pore size of the formation capilaries. If the internal surface of the reservoir is preferetially wet by water, capillarity will cause the water 10 rise to a greater extent above the free water table in a small capillary than in a large one. Consequently the water-oil contact will be higher in the lower permeability sands than in the higher permeability sand.;. The free water table may be defined as the position the oil-water interface would take if capillarity were absent. Since the phenomenon is the capillary rise of water in an oil environment, a derivation of this shold give a relationship between the variables. Fig. 1 is an idealized model of the situation with a uniform bore circular capillary ubstitttting for the tortuous non.circular formation pore. The upward force.; on the column of water will be equated to the forces downward to give the equilibrium situation. forces upward = force downward where r is the radius of the capillary in ceritimetera. a is the interfacial ten4on oil-water in dynes per centimeter, 0 is the

Jan 1, 1953

Jan 1, 1977

By J. R. Low, D. F. Stein

Single crystals of iron have been grown from three different lots of Ferrovac "E" of somewhat different chemical composition by the strain anneal technique. Using a technique to seed the crystal similar to Dunn&apos;s for silicon-iron, it has been possible to orient the crystals grown in both direction and plane of growth. Crystals having the plane of the strip oriented (100) , (110), (111), (112), (123), and (491) have been grown. The growth directions used have been [100], [110], 45 deg from a [110}, and various others of no specific crystal orientation. The usual dimensions of the crystals were 8 by 1 by 0.08 in. Attempts to grow crystals were about 90 pct successful. METHODS of growing single crystals of high purity iron have been reported in the literature.1-4 However, each of these methods was not completely reliable when used on materials having slightly different chemical composition and in some instances a small number of successes were obtained using identical materials. Except for the method used by S. Dohi and T. Yamoshita,1 it has not been possible to reorient single crystals of high purity iron to give any desired orientation. The method to be described has made it possible to grow single crystals from three different lots of material having different compositions, and to orient the crystals with respect to growth direction and surface. STARTING MATERIAL The material used during this investigation was a vacuum melted high purity iron marketed by the Vacuum Metals Corporation designated Ferrovac "E." Three lots of Ferrovac "E" having the following composition were used with equal success: The compositions listed are those of the as-received material; and they may have been modified before the growth of single crystals. Analysis of heat B just before growth and after growth revealed that the heat treatment prior to growth did not change the carbon content, but the oxygen content was changed from 0.0092 pct to 0.0034 pct and the nitrogen content from 0.0003 pct to 0.0001 pct. After growth of the single crystals, the carbon had dropped to 0.001 pct. None of the heat treatments would be expected to change any of the other impurities very markedly. Heat C would be expected to have a metallic impurity content similar to heats A and B. PROCEDURE Ferrovac "E" iron which had been obtained in bar form having a diameter of about 1 in. was rolled into strip for growing single crystals. By passing the 1-in. bar through a cold rolling mill several times, it was reduced to a strip 0.15 in. thick. The strips obtained were then cut into suitable lengths for heat treating (about 9 in. long), annealed at 925°C for 2 hr in dry hydrogen and water quenched. It was then necessary to bake the strip at 200°C for 24 hr in air in order to prevent cracking during further rolling operations. While it was possible to cold roll the 1-in. bar directly to the desired 0.080-in. strip, the intermediate anneal was used because the strip so obtained produced better single crystals. The strip obtained by rolling the 1 -in. bar directly to 0.080-in. strip produced single crystals having a large number of occluded grains. Experiments showed that the optimum reduction in area by rolling prior to the growth of single crystals was about 50 pct. Attempts to grow single crystals from material that had been reduced less than 40 pct were unsuccessful presumably because the matrix did not possess the critical amount of texture necessary for growth. The strip obtained after the rolling operations had very irregular edges which were ground to give a strip with uniform dimensions. The strip was then annealed at 825°C for 3 hr in hydrogen and furnace cooled. Fig. 1 illustrates the grain size obtained. A temperature of 940°C was used for the annealing temperature on one group of strips

Jan 1, 1962

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.&apos; They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,&apos; it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,&apos; the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:&apos; = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By Larry J. Tucker

INTRODUCTION The orebody at Pea Ridge strikes NE-SW and dips at about 800 to the SE. The ore and surrounding rocks are Pre-Cambrian in age. These rocks are usually very competent. Locally strong jointing has caused problems and toward the hangingwall dikes have caused particular problems during or after the open stoping phase of production. About 396 m of sediments lie over the ore. The shape and mineral content of the orebody has been fairly consistent so far with production areas lying from the 1375 to the 2475 levels. The deeper limits of the ore- body haven&apos;t been found yet. The ore is high grade magnetite with a strike length of over 600 m and a maximum width of over 180 m on some levels at the center of the orebody. Production at Pea Ridge for the first three years of operation came from two types of open stopes. The original stopes were recovered with horizontal production rings being drilled and blasted from vertical raises. Later a more typical sublevel stoping method using vertical production rings from one or more drilling sub- levels was used. There were a number of reasons for the selection of open stoping as the initial production method at Pea Ridge. First, it was judged that the ore was not of a block cave quality. After fifteen years of production, this assumption can be verified. There was some concern during the planning days for the potential for high flow rates of water into the mine from aquifers in the sediments lying over the orebody. Dewatering wells from surface and underground were put in as a precaution and nothing came of this potential problem. Open stoping and its resulting pillar structure put off this problem by supporting the sediments a few years longer. For a moderate investment in level development some production from open stoping was quickly realized. The first open stopes were brought in on what was then the bottom mine production level (2275), near the shaft pillar and situated on the footwall. This production practice of stoping on the heels of development from shaft pillar westward and from footwall to hangingwall continued through the open stope phases of production at Pea Ridge for many years. From the standpoint of mine efficiency and pillar stability, this would not seem to be a recommended mining practice. 74 570 w electric slushers, using 1.37 m dippers, pulled the open stope ore out into 18 ton bottom dump cars. Ordinarily five of these cars made up a train, which was pulled to the dump area by a trolley powered electric locomotive. Open stoping had the disadvantage that 100% of the recoverable portions of the orebody had to be developed in order to recover 33% of the ore. 67% of the ore was left behind in a large pillar system. For many years we had no planned method for recovery of these pillars. Mining methods are of course, limited by the existing technology. Advancing technology, coupled with the limited production capabilities of open stoping, low efficiencies and high relative cost early in the history of the operation recommended that other mining methods be looked at. In Sweden, considerable practical experience, coupled with a large amount of theoretical work had become available on sublevel caving. To Pea Ridge it offered the apparent benefits of: 1) The flexibility of diesel powered trackless haulage. 2) The efficiency of two machines to one operator on longhole drilling. 3) A multilevel production picture with a large number of drawpoints for ore recovery. 4) 100% recovery of the mineable portion of the orebody in one production pass, with no pillar recovery problems left behind. This paper outlines the experiments and experiences which Pea Ridge has gone through with sublevel caving from 1967 to this date.

Jan 1, 1981

By W. C. Lilliendahl, G. Meister

Uranium metal with a purity of about 99.9 pct was produced on a large scale by fused salt electrolysis with a material efficiency of about 90 pct. The material efficiency depends mainly on bath composition, electrolysis temperature, electrode smothering, and elutriation during washing of the powder. RESEARCH and development work on fused salt electrolysis carried on by the Westinghouse Lamp Div. Bloomfield, N. J., was done under the Manhattan District Corps of Engineers and later under the Atomic Energy Commission for the commercialization of uranium production for the first atomic pile at the University of Chicago in 1942. From the conception of the atomic bomb project it was recognized that metals with impurity levels having little metallurgical significance would be required. Permissible impurity levels were based on neutron absorption. Of particular significance was boron, which could not be present in amounts exceeding 1 ppm. The electrolytic method as developed in 1930 by Driggs and Lilliendahl,1,2 and later improved, yielded uranium of very low boron and other deleterious impurity content. No other method was capable at that time of producing uranium metal of the required purity.&apos; The low boron content of uranium produced by the electrolytic process resulted from the availability of the reactants which were low in boron content, and from the inherent elimination of boron in the fused salt bath. Since the heart of any electrolytic process is the electrolysis cell, this paper will deal with the development of the original bath composition for the efficient production of uranium from a batch process to one of continuous operation. Emphasis also will be placed on other factors which will affect the material efficiency of the process. With the laboratory cell the material efficiency of uranium powder recovery in the early electrolysis was relatively low, about 35 pct based on the ratio of uranium recovered to uranium added. This early process also had other defects. The electro- lytic bath could not be used continuously. After three runs from a freshly charged crucible, the deposit showed a tendency to slip off the electrode as it was raised from the bath. This condition necessitated pouring the charge every fourth run and preparing a new bath. It was assumed at that time that this condition was caused by the increasing fluoride concentration with each addition of uranium salt, which adected the mobility of the uranium ions. Experimental The electrolysis cells differed in size only. They were of the floating cathode type. The laboratory cells were 21/2 in. ID and 6 in. deep and operated at 30 amp and 5 volts. Production was about 150 g metal powder per 8 hr. The plant cells (5 units) were 9 in. ID x 21 in. deep and operated at 1800 amp at 12 volts. The total production unit was designed to produce 250 lb of uranium powder per 8 hr day. Because of the tendency of uranium fines toward spontaneous combustion, material efficiencies were based only on the recovery of useful coarser metal which could be safely handled. The reported efficiencies are of particular significance only as related to the same group of experimental procedures. At the start of the project no changes were contemplated until previous data could be definitely confirmed. Therefore, the first experiments were with the 50 pct CaCl2-50 pct NaCl mixture. The material efficiency of uranium deposition as a function of the number of electrolyses is shown in Table I. In Table I, the decrease in efficiency at 800°C with number of runs is apparent and confirmed the earlier data. Operating at 900°C enabled the number of runs to be doubled, but before pouring the charge the efficiency of recovery became poor. This test indicated that the improved efficiency might have been caused by an increase in the fluidity of the bath.

Jan 1, 1958

FREderick H. Davis, Electrical Engineer of the Westinghouse Electric and Manufacturing Co., in charge of the plant at Bodie, Cal. (communication to the Secretary): I beg to offer, to complete the information conveyed in Mr. Leggett&apos;s paper, the following report of tests of the electrical efficiency of the power-transmission he has described:

Jan 1, 1895

By C. W. Parmalee

The ideal fuel for burning ceramic wares is the one that, among other characteristics, has little or no sulfur. For that reason wood was long considered the most desirable fuel but its high cost has practically eliminated its use except in regions where it is very abundant or other circumstances warrant its choice. The fuels commonly employed are natural and producer gas, oil, and coal. The last named is undoubtedly the most important, not only in this country but abroad. Occasionally anthracite is used but the larger part is bituminous. The quality of the coal used depends on the kind and the value of the products being manufactured. For some materials, such as common brick, hollow block, etc., the quality of the coal is of less importance than in the manufacture of polychrome terra cotta, pottery, porcelain, etc. It is obvious that in burning clays that contain notable amounts of pyrite, marcasite or gypsum, as is the case with many common clays, the sulfur content of the fuel is of much less importance. The permissible amount of sulfur in the coal used will depend on the kind of product being manufactured. "A good sample1 of coal commonly used in pottery ovens has something like this quantity of sulfur: total sulfur, 1.20 per cent.; sulfur in ash, 0.11 per cent.; volatile sulfur, 1.09 per cent." This is based on English pottery practice. Correspondence with a. number of leading manufacturers in this country has produced the following figures: Sanitary Ware.—(a) 1.0 per cent, maximum, (b) 0.5 per cent. Sewer Pipe.—(a) 1.2 per cent., (b) 1.1 per cent, present run, 3.0 per cent, has been used. Terra Cotta.—(a) 0.5 per cent, basis of contract, 1.0 per cent, approximate. Pottery.—1.0 per cent, contract, 1.5 per cent, probable content. Enameled Brick.—1.3 per cent, maximum, (a) and (6) designate different firms giving figures. Since a pottery kiln for sanitary ware will require about 14 tons of coal for a bum, the quantity of SO2 that will be generated from a 1-per

Jan 1, 1920

By Walter O. Snelling

In the course of some experiments more than five years ago, made for a totally different purpose than the investigation of the oil used, I placed a small quantity of a transparent yellow lubricating oil in a bomb-like vessel and heated it to a relatively high temperature. At the end of the experiment I removed the oil from the vessel and was amazed to find that instead of bearing any resemblance to the oil which I had put in, it now had the appearance of ordinary crude oil. The green color by reflected light and the rich red-brown by transmitted light were so unmistakable as to at once lead to further investigation. I subjected the material to fractional distillation, and the surprise which I experienced at the appearance of the oil, changed to amazement when I found that it yielded, on distillation, 15 per cent. of gasoline and 30 per cent. of burning oil, and that its constitution resembled crude oil quite as much as did its appearance. Furthermore, the gasoline and kerosene distillates which it yielded were of a clear water-white color, entirely without treatment with acid or alkali, and were entirely free from the odor familiar in "cracked" petroleum distillates. The result of this experiment was quite too remarkable to be credited without further confirmation, and I at once filled the vessel with some of the same oil that I had used before, and again heated to about the same temperature that I had previously used, and for the same period of time. Upon opening the vessel and removing the contents I found, not the material resembling crude oil that I had obtained before, but apparently only the same oil that I had put in, somewhat darkened in color, but nevertheless far different in appearance from the material obtained in the previous experiment. Evidently some condition existed in the first experiment that had not existed in the second test, and here began a series of tests in which I sought by the change of one variable after another to arrive at the identical conditions which must have existed in the first experiment. Only the fact that the bottle of heavy oil used in the first test was still in its place,

Jan 1, 1915

Jan 1, 1917

Jan 1, 1926

By John W. Rushton

This month&apos;s article concludes the series with maintenance design considerations in secondary crushing, grinding, and flotation circuits.

Jan 4, 1978

The following officers were elected by the Pennsylvania Anthracite Section of the A. I. M. E. on the evening of June 28th. Chairman, R. V. Norris; vice-chairmen, C. F. Huber, W. G. Whildin, W. J. Richards, Eli Conner; executive committee, Douglas Bunting,. W. W. Engle, Chas. Enzian, J. M. Humphrey, A. B. Jessup, R. A. Quinn; secretary and treasurer, Paul Sterling.

Jan 9, 1919

By John R. Burger

Industrial mineral mines that have recently been opened, or soon will be opened in the northern circumpacific will produce potash in Canada, Mexico, and Thailand; phosphate in the US, Mexico, and Colombia; soda ash in the US; and chromite in the US and the Philippines.

Jan 1, 1982