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By G. D. Gemmell

Effects of solid-sdutidn alloying with titanium, molybdenum, and tungsten at concentrations up to 10 pct on the strength of pure columbium at elevated temperatures (mainly 2000°F) have been investigated by means of creep-rupture, hot-tensile, and hot-hardness testing and recrystallization studies. ThIS paper presents some results from the initial part of a study of the effects of alloying on the high-temperature strength properties of columbium. The elevated-temperature strength characteristics of pure columbium were first studied. Binary alloys of columbium with titanium, molybdenum, and tungsten containing 1, 5, and 10 pct of the solute elements were chosen on the basis of their high melting points, their known solid solubility in columbium, and results of separate oxidation-resistance studies of columbium alloys. EXPERIMENTAL PROCEDURE All the materials used were of highest purity. A typical analysis of the columbium is shown in Table I. Compositions of the alloys are also given in Table I. To evaluate the strength properties of pure co-lumbium and the alloys at elevated temperatures, creep-rupture, hot-tensile, and hot-hardness testing was done on recrystallized material. To prepare the pure metal and the alloys for these tests, 1- 1b buttons were made in a water-cooled copper crucible, inert atmosphere, tungsten arc furnace. Tapered ingots, 3 in. long, were made from these buttons by a skull-casting technique and these were machined to 1/2 in. diam, swaged to 50 pct reduction (pure columbium at room temperature, alloys at lowest temperature possible without cracking, generally in range 1100" to 1800°F) and heated in vacuum (lo-' mm Hg) for 16 hr at 2550°F for re-crystallization and homogenization. The resulting grain diameter was 0.1 to 0.3 mm. The 10 pct Mo alloy casting was not successfully swaged at temperatures up to 1800°F without cracking and was not included in the test program. Creep-rupture testing was done at constant load in vacuum on cylindrical specimens of 0.16 in. diam, using Instron capsules. The pressure at test temperatures was less than 10-1 mm Hg. Hardneas readings taken on the test specimen before and after testing were used as a check on possible gaseous contamination. Hot tensile tests in vacuum on cylindrical specimens of 0.125 in. diam were also made with Instron equipment at a strain rate of 0.067 min.-l. Hot-hardness measurements were taken with a unit constructed at the Du Pont Experimental Station. The test piece, supported on an alumina anvil, and the molybdenum indenter shaft with sapphire tip is heated in a platinum-wound furnace. The load applied to the pyramid indenter is measured by strain gages attached to a proving ring located outside the hot zone. In the measurements reported here the load was I kg. The tester operates in a vacuum of about 10"5 mm Hg and is capable of temperatures up to 1400°C.

Jan 1, 1960

By Denton R. Wieland, Harvey T. Kennedy

The frequency of bubble formation is measured for oils from the East Texas field and the Slaughter field in cores from these fields. East Texas oil was also tested in a Slaughter core. The data checked previous results in that a definite supersatrtration may exist without the formation of bubb1es in periods of observation totaling 158 hours. Measured frequencies varied from zero at supersaturations below 14 psi to 3.1 bubbles/sec/ cu ft of rock at 40 psi supersaturation INTRODUCTION The formation of bubbles is essential in a solution gas-drive reservoir in the displacement of oil. In formations where the basic pore structure consists of fine pores or fractures connected to larger pores or crevices, bubble formation in the fine pores may be the most effective means by which the oil may be displaced, even if secondary methods are applied. The most efficient oil displacement would occur where at least one bubble would form in every pore. As the pressure decreased, the bubbles would expand, due to the gas diffusing into the bubbles, and displace the oil toward the lower pressure area around the wellbore. Kennedy and Olson' have shown that the total number of bubbles formed in a reservoir is primarily dependent upon the rate of pressure drop, the rate of diffusion of gas through oil, and surface area of the rock. The surface tension of the liquid and other characteristics of the rock may also exert an important effect, which would give a different frequency to different rocks and oils and various combinations of different rocks and oils. The purpose of this paper is to present frequency measurements on two rocks and two oils. A hydrocarbon liquid is at equilibrium with gas when it contains the maximum volume of gas in solution that it can have at the prevailing temperature and pressure. If the temperature is maintained constant and the pressure is reduced below the equilibrium pressure, the liquid is supersaturated to the extent of the difference in the two pressures until the gas comes out of solution as a free phase. As shown by previous work, and confirmed in the present investigation, the number of bubbles formed per second increases with an increase in supersaturation. Kennedy and Olson showed that a tenfold increase in the rate of pressure decline resulted in a tenfold increase in the number of bubbles formed per cubic foot of reservoir rock, e.g., for decline rates of 0.1, 1, and 10 psi/day, the number of bubbles formed per cubic foot would be 40, 400, and 4,000, respectively. For another hypothetical system, Stewart, Hunt, and Berry' estimated that for pressure declines of 0.1, 1, and 10 psi/day, the number of bubbles formed would be approximately 10, 100, and 1,000 cu ft of reservoir rock. Their value of bubbles formed is lower than given by Kennedy and Olson; however, the order of magnitude agreed satisfactorily. The rate of diffusion will also affect the number of bubbles formed. If the diffusion coefficient is high, the gas in solution in the oil surrounding a single bubble will tend to diffuse into the bubble rather than forming other bubbles. On the other hand, the formation of more bubbles will tend to occur if the diffusion coefficient is very low. In his thesis dated Aug., 1953, Wood" reports on the frequency of bubble formation in a system consisting of oil and rock from the Rangely field. In the present work, the apparatus of Wood was redesigned to allow greater precision, especially at low supersaturations, where bubble growth is slower, and detection is more difficult.

Jan 1, 1958

By Philip R. Strand

Vermiculite is the name used for those micaceous minerals with a ferromagnesian aluminum silicate composition and the unique property of exfoliating to a low density material when heated. Commercially, the exfoliated products are also called vermiculite, or more exactly, expanded vermiculite. In its exfoliated state, vermiculite serves many markets, chief among them construction, agriculture, horticulture, and general industry. Composition and Properties Vermiculite, in a natural state, has the characteristic mica habit, splits readily into thin laminae, flexible but inelastic. In a mineralogical sense, vermiculite is a hydrated silicate with no exact chemical composition. The structural formula for a macroscopic, trioctahedral vermiculite may be written: [ ] The structure of vermiculite is basically that of a talc, and it could be regarded as a trioctahedral member of the smectite group. Macroscopically, vermiculite displays the prominent monoclinic crystal faces that are commonly marked by lines at 60° and 120°. Hardness varies from 1.5 to 2.8 or more; specific gravities are between 2.1 and 2.8; color is amber, bronze, brown, dark green, or black. When heated quickly to an elevated tempera¬ture, vermiculite expands by exfoliating at right angles to the cleavage, into wormlike pieces (the name vermiculite is derived from the Latin `vermiculare,' to breed worms). This characteristic of expansion, the basis for commercial use of the mineral, is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The increase in bulk volume of commercial grades is 8 to 12 times, but individual flakes may expand as much as 30 times. All expansion occurs at right angles to the basal cleavage. Vermiculite may also be expanded by a number of chemical processes such as soaking in hydrogen peroxide, weak acids, and other electrolytes. There is a color change during expansion that is dependent upon the composition of the vermiculite and furnace atmospheres. Heating in an oxidizing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. The exfoliation of the vermiculite crystal results in large pores being formed between groups of platelets. Thus exfoliation can make available a large increase in void volume without significantly changing the surface area of the platelets. This characteristic is important in the chemical carrier applications of vermiculite. Although there has been much research on the chemical and structural composition of vermiculite, an exact formula and composition cannot be described. This is to be expected since vermiculite derives from a number of different mineral sources. As has been proposed, vermiculite is not a single mineral species, but families of related minerals. Additionally, commercial interest in the end product has resulted in the name vermiculite being applied to the very voluminous, bloated products from calcination of baueritized (bleached) phlogopite. This has also resulted in many names for the specific vermiculite found in a particular deposit. All of this difficulty arises from the nature of its crystal chemistry. Consequently, vermiculite is now thought of as several related variable mineral series rather than a group of related species. The vermiculites have a common silica tetrahedral sheet structure with separating ions. It is now generally agreed that vermiculites must also be regarded as true clay minerals. The properties of the mineral, such as cation exchange capacity, organic complexing ability, and vari-

Jan 1, 1975

By J. Pinto, F. Galasso

THE current emphasis in preparing boron fibers by reduction of gaseous boron compounds on a resistively heated metal wire substrate has renewed interest in the borides of those metals which have relatively high melting points and are available as fine wires. A knowledge of the structures and properties of the borides, which are formed when boron diffuses into the metal core during boron deposition, can be of assistance in the understanding of the boron fiber formation process and the fiber properties. Many of these borides are well-known and their properties have been measured. However, when an unidentified boride is found in the core, it may be difficult to establish its composition because of the small amount of material available, the preferred orientation effects on the reflections in its X-ray pattern, and the possible overlap of X-ray reflections if several borides are present in the core. For example. the proper indexing of the X-ray pattern of WB4, which was formed in the tungsten substrate core during boron fiber formation, was accomplished only after small single crystals of this boride were grown and X-ray precession investigations were conducted.' This note presents the results of a study of the phases formed in the core when tungsten, tantalum, and molybdenum metal wires were used as substrates in the boron fiber preparation process with particular emphasis on the identification and characterization of a higher boride of molybdenum analogous to WB,. Boron was deposited on resistively heated stationary 0.0012-in.-diam tantalum, tungsten, and molybdenum wires at 1050°C for various times up to 60 sec using boron trichloride and hydrogen as the reactant gases. After 60 sec of boron deposition the fibers were approximately 0.006 in. in diam. Examination of photomicrographs of fiber cross sections showed that the boron had diffused nearly to the center of the tungsten and molybdenum cores in 15 and 30 sec, respectively, and only halfway to the center of the tantalum core in 60 sec. X-ray diffraction photographs of the fibers indicated that it was also after 15 and 30 sec deposition times that the tungsten and molybdenum metal reflections, respectively, had disappeared from the X-ray patterns of the fibers. The patterns of the boron fibers produced using tantalum wire as a substrate showed that amorphous boron, TaB2, and tantalum metal were present after a few seconds deposition time and remained even after deposition times of 60 sec. Until a deposition time of 15 sec was reached, the tungsten substrate fibers contained amorphous boron,273 6WB, W2B5, and WB4 as well as tungsten metal, while the molybdenum substrate fibers contained amorphous boron, MoBa, Mo2B5, and molybdenum metal for deposition times up to 30 sec. Just before the molybdenum metal pattern disappeared, a pattern similar to that of WB, appeared, suggesting that a phase, MOB,, isomorphous with WB,, was present in the fiber. This same pattern was obtained from the product formed by heating a mixture of molybdenum metal and excess boron powder in a boron nitride crucible at 1960°C in an argon atmosphere. As was the case with the WBn pattern, this pattern could best be indexed on the basis of a hexagonal unit cell rather than the tetragonal unit cell Chrktien and Helgorsky reported for ~0~4,~ see Table I. The unit cell parameters for MoB4 were calculated to be a, = 5.214A, co = 6.358A. Assuming the space group P63/mmc and positions5 2M01 in 2b and 2MoII in 2c found for tungsten in WB~,' a logical structure for MOB, was determined using geometrical considerations to place the boron

Jan 1, 1969

By Oliver Bowles

ALTHOUGH Oliver Bowles retired as chief of the nonmetal economics division of the Bureau of Mines last year, that retirement has not lessened his active interest in the field of nonmetallic minerals, in writing, nor in his hobby, cultivation of African violets. Excellent co-ordination of the timing of a professional meeting and a flower show permitted him on at least one occasion to attend technical sessions and take in the African violet exhibition which happily arrived simultaneously in one city. Dr. Bowles celebrated his seventieth birthday on Jan. 10, 1947, and

Jan 1, 1948

C. W. Kempton, Oro Blanco, Ariz.: In his interesting paper, Mr. Ingalls refers to reports of tin-deposits near Sain Alto, Zacatecas, Mexico. During 1891 I made some personal examinations of these deposits. They are, for the most part, located from 10 to 30 miles west of the town, in the Sierra del Fraile.

Jan 1, 1896

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K's) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.' In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By C. L. Sollenberger, Will Mitchell, Ford F. Miskell

Heat treatment of ore prior to comminution reduces power requirements for grinding, reduces grinding media wear, and improves recovery of iron values from a typical Minnesota magnetic taconite. Test data demonstrating this, as well as an analysis of the economics of commercial application of the technique, are presented. THE taconites in general are hard, tough ores, difficult to grind. Liberation of iron mineral constituents usually is accomplished by grinding the ore through at least 100 mesh, and often it has been found necessary to grind substantially through 325 mesh to achieve satisfactory recovery and grade in the concentration process. Because of the fineness of grind required and the enormous tonnages of material contemplated for treatment in the future, costs resulting from grinding media wear and power consumption, together with capital investment required for comminution, approach astronomical figures. Economy in any one of these elements per ton of material ground could very well reflect a considerable saving to the ferrous industry in yearly costs. With this in mind, the Research Laboratories of Allis-Chalmers Manufacturing Co. have launched a program to discover means of effecting this economy. The initial phase of the work as described here deals with a heat treatment of crushed raw ore, followed by thermal shock in cooling, for the preparation of rod mill feed. Several investigators1-" ave noted an improvement in the grindabilities of ores treated in this manner. One investigator2 subjected low grade iron ores to heat treatment in an electric furnace. Basing his conclusions on screen analyses of crushed products, he observed that treated ore was more easily crushed than the untreated. He reported that observation of the treated and untreated ore through a microscope revealed cracks following the grain boundaries in treated ore, whereas no cracks were present in untreated ore. However, few if any have quantified the improvement in terms of total hp hours saved, reduction of wear of grinding media, or reduction of capital costs of grinding equipment involved. By means of Bond rod mill and ball mill grindabilitiesh nd by comparative wear tests, the conditions maintained during this investigation have been definitely evaluated. Heat treatment experiments have been made on a batch scale in a muffle furnace, followed by continuous scale experiments in a rotary kiln under various conditions of temperature, atmosphere, retention time, and quenching to determine the combination that would give the greatest improvement in the grindability of a taconite without affecting adversely the magnetic susceptibility of the magnetite. From these data, relative costs have been calculated for grinding both untreated and heat- treated ore on a basis of plant capacity of 120 tons per hour. Heat requirements for a rotary kiln, as well as the kiln capacity required for the treatment, have been estimated. For these tests 50 tons of ore were obtained from the Aurora mine of the Erie Mining Co., Hibbing, Minn. The ore was reported7 to have been selected from the magnetic portion of the lower chert horizons. An average chemical analysis of' this portion is shown in Table I and an approximate mineralogi-cal analysis is shown in Table 11. No attempt was made to differentiate between the various silicates because the compositions vary widely on the different horizons and depend on the degree of oxidation. Minnesotite, however, is the predominant silicate. The siderite grains were dispersed throughout the ore but were essentially associated with the rock-forming minerals. In a series of preliminary tests in which batches of —6 mesh ore were heat-treated in a muffle fur-

Jan 1, 1953

By J. Szekely, Robert G. Lee

Calculations are presented for the prediction of the combined radiative-convective heat loss from molten steel held in a ladle, covered by initially molten slag. A mathematical formulation is given and numerical solutions are presented of the resultant partial differential equation. It is shown that a slag layer of about 2 to 3 in. thick would prevent any significant heat loss from the top metal surface for Periods of up to 1 hr. For thinner slag layers (or in the absence of the protective slag) appreciable heat losses would occur; plots given in the paper allow the quantitative evaluation of the fall in the metal temperature due to this heat loss. The ironmaking-steel processing operation involves several intermediate steps where the molten metal is held or transfered in ladles. The quantitative assessment of the heat losses occurring under these conditions is of considerable importance in process design considerations since the temperature of the metal may have to meet rigid specifications in any given part of the processing sequence. While the metal is held in a ladle, heat is lost by two mechanisms: i) by conduction into the ladle walls; ii) by radiation and convection from the top surface. Calculations relating to the conductive heat loss, are readily made and information may be found in the literature both on data pertaining to metallurgical situations and on the techniques that are available for performing additional computations.'-3 The evaluation of the combined convective-radiative heat loss is less straightforward, especially when there exists a protective slag layer covering the metal. In this latter case, as the top slag surface loses heat partial solidification may occur and the latent heat thus given up by the slag may represent an effective barrier to the heat loss from the metal. A semiquantitative assessment of the role played by the slag in preventing heat loss from the metal has been made in a previous paper,4 where it was shown that a slag layer 6 in. thick would act as a near-perfect insulator for periods of up to 2 hr. However, this first paper reported on an essentially preliminary investigation that considered only one slag layer thickness; furthermore, the boundary conditions used for the calculations were somewhat restrictive since no allowance was made for changes in the metal temperature. The purpose of this second paper is to extend the scope of the preliminary investigation previously reported by: i) considering several slag layer thicknesses; ii) allowing for variations in the metal temperature; and finally iii) by performing calculations on the net loss from the metal rather than from the slag surface. FORMULATION Consider a slag phase extending from y = 0 to y = L1, covering a metal phase that occupies the region extending from y = Ll to y = L, as illustrated in Fig. 1. Denote the slag and metal temperatures by TS and Tm and assume that initially both slag and metal are molten, having a uniform temperature Ti. At time = zero the surface represented by the y = 0 plane (top slag surface) is brought into contact with cold air, the temperature of which is given as T Thus for time > zero, heat will be transfered from the slag to the air by natural convection and thermal radiation; as a result of this heat loss the slag temperature will fall and after some time a solid phase is formed and a solidification boundary (more realistically described as a zone) will move progressively from y = 0 toward y = L1. Once the region of temperature gradients, moving ahead of the solidification zone, reach the slag-metal interface (y = L1) there will be a net transfer of heat from the metal through the slag to the cold air, across the y = 0 plane. In the formulation of moving boundary problems, involving phase changes that require computer solution, it is convenient to represent both phases by a single equation, making allowance for the latent heat of solidification by assigning an appropriate temperature dependence to the specific heat content. Thus the energy equation for the whole of the slag may be written as follows:

Jan 1, 1969

By G. F. Bolling

STUDIES of grain boundary migration in zone-refined metals have all shown that the rate of migration is greatly reduced by small added solute concentrations. However, it is apparent that a difference exists between boundary migration during normal grain growth and single boundaries migrating in a bicrystal to consume a substructure. To effect the same reduction in velocity in the two cases, much more solute is required for grain growth than for the single boundary experiments. One case is available for direct comparison; both Bolling and winegardl and Aust and utter' added silver and gold to zone-refined lead to study grain growth and single boundary migration, respectively. For comparable reductions in migration rates, about 500 times more solute was required to retard grain growth than to retard the single boundaries. A reason for this difference is suggested here. The rate of grain boundary migration is dependent on solute concentration and must therefore also depend on the solute distribution; i.e., regions of higher solute concentration encountered by a moving boundary must produce greater retardation and thus could determine any observed rate. A dislocation substructure can be the source of a nonuniform solute distribution since it can attract an excess concentration of certain solutes. In fact, it is probable that the solutes which impede grain boundary migration most would segregate most severely to a substructure for the same reasons. Thus a dislocation substructure present in a crystal being consumed could locally magnify the concentration of solute confronting an advancing grain boundary. In the single boundary experiments a low-angle substructure, within single crystals obtained by growth from the melt, was used to provide the driving force to move a grain boundary; in grain growth, no substructure of this magnitude was present. The increased solute concentration at subboundaries should be given approximately by C, = G e c,/kT, where t, is a binding energy and CO the bulk concentration. To account for the difference between the two experiments in the Pb-Ag and Pb-Au cases, C, must be the concentration impeding the single boundary migration, and a value of t, = 0.25 ev is necessary. This is reasonable, even though calculation on a purely elastic basis gives t, = 0.12 ev. because electronic effects must enter for silver and gold in lead. The compound AuPbz forms3 and the metastable compound AgrPb has been reported to nucleate at dislocations prior to the formation of the stable, silver-rich phase.4 Other observations support the hypothesis that a magnified solute concentration impedes the single boundary migration. For example, some crystals were grown by Aust and Rutter at concentrations of ~ 0.1 wt pct Sn and 2 x X at. pct Ag or Au which exhibited a cellular substructure, and in these crystals no boundary migration was observed. It is therefore evident that the higher concentrations at cell boundaries drastically inhibited migration. Inclusions would not have been responsible for this inhibition since according to recent work on cellular segregation,5 no second phase should have occurred in the segregated regions at the cell boundaries for the conditions of growth used, at least in the Pb-Sn system. In the purest lead, only the "special" boundaries observed by Aust and Rutter gave rise to the same activation energy as that obtained in grain growth. It is reasonable to suppose that the structure of special boundaries does not favor segregation at low concentrations and thus solute, or an inhomogeneity in its distribution, would have no effect. Random boundaries, on the other hand, are affected by solute and the substructure would enhance residual concentrations in the zone-refined lead, leading to a higher activation energy. It is clear, even without a detailed theory, that the apparent activation energies and exact solute dependence in the two experiments must be different as long as the non-uniform solute distribution produced by the substructure is important. Recrystallization experiments should also be susceptible to the same kind of local segregation at subboundaries or disloca tion cell walls; a suggestion similar to this has been made by Leslie et al.' Following the arguments presented here, the effects of a given solute concentration would be like those observed by Aust and Rutter if segregation occurred, and like those of grain growth otherwise. This work was partially supported by the Air Force Office of Scientific Research; Contract AF-49(638)-1029.

Jan 1, 1962

By Arnulf Muan, R. W. Taylor

Activities of iron in Fe-Pt alloys have been dctermined by equilibrating mixtures of platinum metal and iron oxide at known oxygen Pressures in a thermobalance at 1300°C. Conzpositions and iron activities of the oxide phase at equilibrium are known from previous work, and compositions of the Fe-Pt alloy phase formed at equilibrium were detcvt?zined from the observed weight changes of the samples. The activity curve obtained shows a strow negative deviation from Raoult's law. THE present investigation was undertaken as part of a research program dealing with phase equilibrium relations existing among the oxides of iron and titanium at 1300°C. At low oxygen pressures of the gas phase in equilibrium with these oxides, the iron activity of the system is high, and considerable alloying of iron with the platinum used as a container material takes place. Thermodynamic data for Fe-Pt alloys at 1300°C are needed in order to evaluate quantitatively the extent of such reactions. Larson and chipmanlhave determined activities of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with CaO-iron oxide-SiOzmelts in which the iron activities were known. Compositions of the resulting Fe-Pt alloys were determined by chemical analysis. Mundiath and Gerassimov2 have studied thermodynamic properties of Fe-Pt alloys by electromotive force measurements in the temperature range 550" to 1000°C. The experimental method used in the present investigation is a slight modification of that used by Grube and Ratsch3 in studies of NiCr-alloys. 1) EXPERIMENTAL METHOD 1) General. Mixtures of platinum metal and iron oxide were equilibrated at 1300°C in atmospheres of known oxygzn przssures, and the course of the reactions was followed by measuring the weight changes of the mixtures. The principles involved in the derivation of composition-activity relations from these measurements are illustrated by the composition triangle for the system Fe-FeZO3-Pt shown in Fig. 1. Take as an example a mixture of FeZO3 (hematite) and platinum such that the total composition is represented by point T. If this mixture is heated to 1300c in air (poz = 0.21 atm) and the oxygen pressure is then reduced gradually, the oxygen content of the oxide phase decreases and increasing amounts of iron enter the metal phase. As the oxide phase and the metal phase for all practical purposes are insoluble in each other, their compositions are represented by points moving toward Fe along the joins Fe-Fe,03 and Fe-Pt, respectively. The total composition of the mixture during this process also changes, but only with respect to oxygen content, because the vapor pressures of iron and platinum are negligible at 1300°C. Hence the change in total composition is described by a straight line (constant Fe/Pt ratio) radiating from the 0 apex of the composition triangle Fe-Pt-0, of which the triangle in Fig. 1 is a part. Only one such line ("oxygen reaction line", T-T",) is shown in Fig. 1. The total composition of the alloy-iron oxide mixture at any instant must, in addition, be located on the straight line (conjugation line) connecting the two points representing the compositions of the two coexisting phases. It therefore follows that the total composition of the mixture at any instant is represented by the point of intersection between the conjugation line and the oxygen reaction line. An example of the situation prevailing at a chosen oxygen pressure, po2, is shown in Fig. 1 by points a' (alloy composition), b' (oxide composition) and T' (total composition). Point b' is known from the work of Darken and Gurry,4 and point T' is experimentally determined by the observed weight change of the mixture (distance T-T). Hence, point a', the composition of the alloy, is determined from the above data as the intersection between the join Pt-Fe and the extension of the straight line bl-7'. The activity of iron in the alloy at equilibrium is identical to that of the iron oxide phase, if the same

Jan 1, 1962

By J. J. Scott

This investigation utilizes three dimensional photo-elastic techniques to determine the stress distributions in the pillars and the roof of a room and pillar mine model. Castolite plastic was used for the construction of the model in which a stress pattern was developed by the stress freezing process. Analysis of the stress pattern was accomplished by observation of points in slices from the model with a polariscope and solving the data thus obtained by the shear-difference method. Slices through the centerline, edge of pillar and centerline of span were investigated. The results of this work provide information on the overall stress distribution in points of stress concentration in compression, shear and tension, show relative magnitude of stress throughout the model and indicate directions of the most important stress values. A generalized roof bolt pattern is developed for room and pillar mines based on the stress distribution. A digital computer was used in the reduction of data and proved to be extremely useful for investigation of this type. Underground excavations disturb the equilibrium of the earth's crust and a core of fracture, or altered stress distributions exists around the openings. This fact is well known by mining operators and investigators in the rock mechanics field. Analysis of the stress distribution in the areas around mine workings is a most difficult problem and one which has no simple and direct solution. Some of the approaches used by investigators in attempts to study stress distribution around mine openings involve mathematical analysis, photoelastic techniques, statistical analysis, model studies on brittle materials and observation of fracture patterns. Models involving imbedded strain gauges, gelatin models using imbedded strings to show internal movement, and many other unique laboratory techniques are employed. Work is also being done in mining operations where load cells, strain gauges, photostress material, convergence plugs, dynamic plugs, etc., are used to measure strain which can in turn be used to obtain stress. Some of these devices measure strain from which stress may be derived. All approaches to the solution of stress distribution are hampered by the fact that the earth is not a homogeneous, isotropic and elastic media. Geologic faults, fractures, bedding planes, vugs, variations in material composition, variations in grain size and structure, etc., make it extremely difficult to obtain results which can be universally applied to mining operations. The purpose of this investigation will be to demonstrate the use of three-dimensional photoelastic techniques to obtain the stress distribution in the pillars and roof of a room and pillar mining operation. This method utilizes full analysis of interior points, and thus it may be that small tensile or shear stresses found in the investigation will prove to be of greater significance than the more obvious points of stress concentration found by two-dimensional techniques. A digital computer was employed to simplify and to shorten the time necessary to obtain final results. Application of the computer to problems of this type may enable future investigators to attempt more elaborate analyses than have been previously considered feasible. THEORY Three Dimensional Stress Analysis-Shear Difference Solution:' Photoelastic studies are based on the fact that an optically isotropic transparent solid becomes optically anisotropic when subjected to forced deformation; the degree of optical anisotropy being proportional to the deformation of the material. There are two fundamental laws which govern photoelasticity: 1) Light is polarized in the directions of the principal stress axes, and is transmitted only on planes of principal stress. 2) The difference in principal stresses is proportional to the difference in the indices of refraction along the planes of principal stress. One method used in three-dimensional photoelastic work is to examine a slice of the object by normal incidence and oblique incidence. In normal incidence,

Jan 1, 1964

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.' Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2'4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy's equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.' were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By T. R. A. Gokcen

THE possibilities of separating and purifying metals by high vacuum distillation were examined by Kroll.1 He suggested vacuum treatment for the removal of zinc from the lead produced after Parkes desilverizing. The St. Joseph Lead Co. developed the first commercial vacuum dezincing process at their Herculaneum refinery, as described by Isbell.² The Broken Hill Associated Smelters at Port Pirie, Australia, has, after several years of pilot plant operations and fundamental investigations, developed a continuous process, which will be described briefly in a forthcoming publication." As the full-scale continuous vacuum dezincing plant at Port Pirie is still experimental, publication of full practical details of the plant will be deferred until the unit is operating as a normal part of the continuous refinery. This paper deals only with theoretical aspects of vacuum distillation processes, with particular reference to vacuum dezincing. The method of mathematical analysis is of general interest as it may be applicable to other metallurgical separations which have been investigated recently.4-6 Evaporation Processes At about atmospheric pressure, or higher, most liquids possess a boiling point—a temperature at which any heat put into the liquid is absorbed only as latent heat, not as specific heat. If a steady heat input is supplied, the liquid's temperature rises to this value, then remains constant while bubbles of vapor form beneath the surface. The rate of evaporation is determined solely by the rate of heat transfer to the liquid; the temperature of boiling is determined by the partial pressures of the volatile constituents in the liquid, and the total pressure above the surface. If the rate of heat transfer to the liquid is increased, the temperature remains constant, and the rate of boiling increases. When evaporating metals under vacuum, however, the partial pressures concerned are generally so small that boiling does not occur, because at even a fraction of a millimeter below the surface the hydrostatic pressure is usually too great to permit the formation of a pocket of vapor. In addition, the high thermal conductivity of metals tends to prevent the local superheating which is necessary for bubble formation.' Although this effect is doubtless also exerted when boiling metals at higher pressures, the magnitude will be less because the degree of superheat required to form bubbles is very much less at the higher temperatures involved. Under vacuum, therefore, evaporation of volatile constituents takes place only from the exposed surface, and the rate of evaporation depends upon the surface area, the surface concentration of volatile constituents, the surface temperature, and the partial pressures of volatile constituents immediately above the surface. If the heat input is raised above a certain level, the effect is not to increase the evaporation rate at constant temperature, but to raise the temperature of the liquid until at some higher level an increased rate of evaporation (and thus of latent heat absorption) again balances the heat input rate.? Many substances (including metals) have a very large intrinsic evaporation rate at quite low temperatures—far below their normal boiling points. However, at atmospheric pressure, the large numbers of atoms evaporated are almost completely deflected back into the liquid (or solid) surface by air molecules. Thus the back condensation rate is practically equal to the gross evaporation rate, and the net evaporation rate is practically zero. It can therefore be seen that an overall distillation rate depends not only upon the intrinsic evaporation rate, but also upon the ability of the volatile atoms to move away from the evaporating surface. This movement is facilitated by the provision of a condensing surface close by. Vacuum Distillation: The function of the vacuum above the evaporating surface is to remove foreign molecules, so that the chances of deflection of an evaporated atom back into its source are reduced. When the residual gas pressure is reduced so far that the evaporated atoms have a high probability of reaching a nearby condensing surface without suffering collision with a foreign molecule, the state of affairs is termed "molecular distillation." This process is practiced commercially today for the purification of numerous organic chemical products of high unit value, but not, to the writer's knowledge, for any metallurgical separation. When the degree of vacuum produced in a still is not sufficient to promote molecular distillation, then the evaporated molecules must diffuse through the

Jan 1, 1954

By W. R. Hudspeth

AS an outgrowth of its spodumene recovery operation at Kings Mountain, N. C., Foote Mineral Co. has been recovering a heavy mineral by-product. Foote leased this idle plant in 1951, reactivated it, using a new spodumene recovery process, and purchased plant and properties in October 1951. While the operation at Kings Mountain is primarily concerned with the production of spodumene concentrate, pilot plant work determined that the pegmatites also contained heavy minerals including cassiterite. Plans were made to recover the heavy minerals as a by-product and the flowsheet incorporated these facilities when the mill was modified for the new spodumene recovery process. The orebodies consist of spodumene, feldspar, quartz and mica. Apatite, tourmaline, and beryl are present in small quantities. The wall rock is pre- dominantly hornblende shist. The heavy minerals, including cassiterite, columbite, pyrrhotite, monazite, pyrite, and rutile represent about 0.2 pct of the ore. The fine-grained heavy minerals are disseminated throughout the dikes, apparently unassociated with the spodumene. The pegmatites are quarried and secondary breakage is by mud-capping and block-holing. Power shovels load into trucks transporting the ore to a coarse ore bin. A Telesmith 10x36-in. apron feeder delivers the ore to an 18x36 in. Traylor Jaw crusher adjusted to discharge -3 in. product to a primary conveyor. The conveyor delivers to a 4x5-ft Tyrock single deck vibrating screen using 3/4 in. cloth. The screen undersize is elevated to the crushed ore bin. Screen oversize goes to an Allis-Chalmers Hydrocone Crusher fitted with 4 in. concave and set to deliver approximately 66 pct minus 3/4 in. The crusher discharge returns to the primary conveyor. The crushing and screening installation has a capacity of about 60 tons per hour. Spirals The crushed ore is delivered at a rate of 350 tons per day to two 6x8-ft Hardinge Pebble Mills, equipped with 20 mesh Ton-Cap trommel screens. The screen oversize is pumped to a 12-in. hydroclone for primary desliming. The hydroclone underfl spirals. There is no heavy mineral loss in the hydro-clone overflow. The spirals bank consists of eight 5-turn Model 24-A Humphreys Spirals. The top port and the last four ports of each spiral are blanked, the remaining nine port splitters are adjusted to remove about 5 pct feed weight. The heavy mineral rougher concentrates are upgraded on a Deister Overstrom table. The spiral concentrates contain approximately 4 pct heavy mineral, and the spiral reject, which goes to another section of the plant for spodumene recovery, contains about 0.03 pct heavy mineral. There is an interesting feature in the spirals installation. An adjustable splitter mounted on the discharge boxes splits out a mica fines product containing very little heavy mineral. The mica product is cleaned by spiralling and screening. Thus the spirals recover two products; mica, and a heavy mineral rougher concentrate. Table Treatment The rougher spiral concentrate goes to a Deister Plato table, modified to receive a Deister-Overstrom No. 6 rubber cover with sand riffles. The table is operated with a 5/8 in. stroke, 270 strokes per minute, and a slope of 1/2 in. per ft from feed to tailings side. There is no slope adjustment from motion to concentrate end. Wash water consumption is relatively high, since the large spodumene grains tend to report with the fine heavy minerals. A middling band about 4 in. wide is maintained in order to produce clean concentrate. The middling, representing about 10 pct of table feed, is recirculated by air-lift. A band of concentrate grade coarse spodumene occurs just below the middling. This is removed and delivered to concentrate storage. The table tailing, containing approximately 0.7 pct heavy minerals, is returned to the spodumene feed preparation circuit. The heavy mineral table concentrates are approximately 45 pct cassiterite, 33 pct columbite, 14 pct pyrrhotite and 8 pct monazite, together, with some rutile, pyrite, and copper from blasting wire. Concentrate is collected at 24 hour intervals. and dried. If the concentrate remains in wet storage appreciably longer surface oxidation takes place which seriously interferes with the subsequent magnetic separation process. About 150 lb of heavy mineral concentrate is produced per 24 hours and shipped to the company's plant at Exton, Pa. for final separation into tin and columbium concentrates.

Jan 1, 1952

By C. H. Li, S. H. Bendel, J. A. Sartell

Small additions of Mg to a 62 Cu-38 Ni alloy reduce the oxidation yates drastically between 500° and 850°C. Metallographic examination of the oxide scale disclosed a continuous network, identified by X-ray diffraction as (Ni, Mg)O solid solutions, located along the former alloy grain boundaries. This network acts as a barrier to diffusion. It is thought to result from the segregation of mg to the alloy grain boundaries. Oxidation occurs preferentially in these regions because of the presence of this more active element. To substantiate these ideas, homogenized alloys ulere oxidized. No oxide network was produced and oxidation rates were the same as for the parent 62 Cu-38 Ni alloy. An interesting aspect of the oxidation of the 62 Cu-38 Ni alloy previously described by the present authors, is the relationship between oxidation kinetics and changes in the microstructure of the oxide.' The oxide scale on these alloys consists of two layers: a thin layer of CuO outside a much thicker layer of Cu20 in which particles of NiO are dispersed. In addition, immediately beneath the oxide-metal interface there is an internally oxidized zone in which NiO particles are dispersed in a copper-rich alloy matrix. Experimental observations on the growth of the individual layers under isothermal conditions have led to the conclusion that the rate-determining step in the oxidation of this alloy is the diffusion of anions through the Cu20 layer. It has been found that this diffusion rate is increased by the recrystallization of the outer CuO layer. Willardson and Gorton have reported that the addition of magnesium to the 62 Cu-38 Ni alloy causes a decrease in the oxidation rate.2 The present investigation was undertaken in order to determine the mechanism by which magnesium additions improve the oxidation resistance of the 62 Cu-38 Ni alloy. EXPERIMENTAL PROCEDURE Fifty-gram ingots of Cu-Ni alloys were prepared by vacuum melting materials of 99.999+ pct purity. These ingots were then remelted in a He atmos- phere and magnesium added in the form of a previously prepared and analyzed Cu-Mg master alloy. This procedure was necessitated by the high reactivity of pure magnesium at high temperatures. The proportion of the alloying elements was adjusted so as to obtain alloys with the desired magnesium content while maintaining a Cu-Ni ratio of 62 :38 by weight. (All alloy compositions will be given in weight percent.) Since it was considered desirable to study the oxidation of only single-phase, solid-solution alloys, it was necessary first to determine the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy. A series of melts with various magnesium contents was made, homogenized by annealing for 48 hr at 975OC, then cooled in the furnace. Metallographic samples were prepared, etched in a potassium dichromate solution and examined at XI500 for the presence of a second phase. The alloys were then chemically analyzed and it was found that the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy was 1 pct Mg. The ingots containing less than 1 pct Mg (0.19, 0.29, 0.58, and 0.87 pct Mg) were cold-rolled down to thicknesses suitable for oxidation experiments and specimens for gravimetric studies were cut to dimensions of 3.0 by 1.5 by 0.05 cm, specimens for inert marker studies, 0.6 by 0.6 by 0.17 cm. These were heat-treated in a protective atmosphere at a temperature (975" C) well above the oxidation temperatures and furnace-cooled to insure structural stability of the alloy during oxidation. Immediately prior to oxidation, the specimens were chemically cleaned by immersion for 1 min in a solution of 2 parts nitric acid, 1 part acetic

Jan 1, 1961

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K's) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.' In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By Will Mitchell, Ford F. Miskell, C. L. Sollenberger

Heat treatment of ore prior to comminution reduces power requirements for grinding, reduces grinding media wear, and improves recovery of iron values from a typical Minnesota magnetic taconite. Test data demonstrating this, as well as an analysis of the economics of commercial application of the technique, are presented. THE taconites in general are hard, tough ores, difficult to grind. Liberation of iron mineral constituents usually is accomplished by grinding the ore through at least 100 mesh, and often it has been found necessary to grind substantially through 325 mesh to achieve satisfactory recovery and grade in the concentration process. Because of the fineness of grind required and the enormous tonnages of material contemplated for treatment in the future, costs resulting from grinding media wear and power consumption, together with capital investment required for comminution, approach astronomical figures. Economy in any one of these elements per ton of material ground could very well reflect a considerable saving to the ferrous industry in yearly costs. With this in mind, the Research Laboratories of Allis-Chalmers Manufacturing Co. have launched a program to discover means of effecting this economy. The initial phase of the work as described here deals with a heat treatment of crushed raw ore, followed by thermal shock in cooling, for the preparation of rod mill feed. Several investigators1-" ave noted an improvement in the grindabilities of ores treated in this manner. One investigator2 subjected low grade iron ores to heat treatment in an electric furnace. Basing his conclusions on screen analyses of crushed products, he observed that treated ore was more easily crushed than the untreated. He reported that observation of the treated and untreated ore through a microscope revealed cracks following the grain boundaries in treated ore, whereas no cracks were present in untreated ore. However, few if any have quantified the improvement in terms of total hp hours saved, reduction of wear of grinding media, or reduction of capital costs of grinding equipment involved. By means of Bond rod mill and ball mill grindabilitiesh nd by comparative wear tests, the conditions maintained during this investigation have been definitely evaluated. Heat treatment experiments have been made on a batch scale in a muffle furnace, followed by continuous scale experiments in a rotary kiln under various conditions of temperature, atmosphere, retention time, and quenching to determine the combination that would give the greatest improvement in the grindability of a taconite without affecting adversely the magnetic susceptibility of the magnetite. From these data, relative costs have been calculated for grinding both untreated and heat- treated ore on a basis of plant capacity of 120 tons per hour. Heat requirements for a rotary kiln, as well as the kiln capacity required for the treatment, have been estimated. For these tests 50 tons of ore were obtained from the Aurora mine of the Erie Mining Co., Hibbing, Minn. The ore was reported7 to have been selected from the magnetic portion of the lower chert horizons. An average chemical analysis of' this portion is shown in Table I and an approximate mineralogi-cal analysis is shown in Table 11. No attempt was made to differentiate between the various silicates because the compositions vary widely on the different horizons and depend on the degree of oxidation. Minnesotite, however, is the predominant silicate. The siderite grains were dispersed throughout the ore but were essentially associated with the rock-forming minerals. In a series of preliminary tests in which batches of —6 mesh ore were heat-treated in a muffle fur-

Jan 1, 1953

By J. B. Agan, R. J. Fernandes

This paper utilizes the layered-system approach, modified to include areal sweep efficiency, to determine the miscible-slug size required and to predict the perfort7zance of a miscible-slug process in a highly stratified reservoir having a permeability variation of 0.76. The slug size in each layer was determined from theoretical calculations and laboratory data which showed that, to maintain miscibility in the reservoir, the slug size had to be 8.2 per cent of the floodable hydrocarbon pore volume. Economic considerations, however, such as the value of the miscible product injected, the cost of injection and the cost of reprocessing the miscible product, limited the amount of miscible product which could be injected into the lower-permeability layers. This resulted in subjecting only 60 per cent of the reservoir to a slug size sufficient to maintain miscibility. Utilizing the relationship of producing gas-oil ratio and areal sweep efficiency as a function of pore volume injected (as obtained from data published by Dyes, Caudle and Erickson2), the theoretical performance was determined. This prediction is compared with actual performance to date. Actual performance reflects an increasing percentage of tniscible product in the produced fluid to a particular level, which remains static for a short period and then increases again to a higher level. This performance suggests that the reservoir has performed as a layered system. It is concluded that the layered-system approach can be used to predict performance in a highly stratified reservoir and that economic consideration is a limiting factor in determining the amount of the reservoir which can be miscibly swept. INTRODUCTION The Paloma zone in the Paloma oil field, Kern County, Calif., is comprised of several sand members separated by siltstone, shale and/or cherty sections. Rapid facies changes within the zone indicate that the sediments were deposited in a "near shore" environment. As a result, the Paloma sands have a high permeability variation, and the Paloma zone is comprised of several sand reservoirs. Since one of the sand reservoirs containing crude oil was not receiving the benefits of gas injection, consideration was given to recompleting certain wells to isolate the sand in order to perform a miscible-phase injection project and, thereby, to increase its ultimate oil recovery. Before proceeding with the project, a review of the literature was made to determine the miscible-slug size that would be required to maintain miscibility throughout the displacement process. Although the review showed that considerable information was available for homogeneous systems, insufficient information was available to determine slug-size requirements and to predict performances for a highly stratified reservoir. This paper has been prepared to describe the method used to determine the miscible-slug-size requirement and to predict the performance of the miscible-phase injection project initiated in the Paloma oil field. Although the Paloma project has only been in operation since Aug., 1958, sufficient production history has been obtained so that a comparison can be made with the predicted performance. DESCRIPTION OF RESERVOIR The reservoir in which the miscible-phase project was initiated in the Paloma field is shown on Figs. 1 and 2. Reservoir properties are as follows: average sand thickness, 43 ft; porosity, 19.1 per cent; water saturation, 47.2 per cent: oil viscosity, 0.328 cp; reservoir temperature, 250°F; reservoir pressure, 3,500 psi: gas saturation, 21.2 per cent at time of miscible product injection; and total net hydrocarbon pore volume, 19,993,000 reservoir bbl. LIMITATIONS The method described herein utilizes a layer-system approach, where injection into and production from each layer is assumed to be proportional to the layer's fractional capacity. The effects of increased fluid mobility on injection and production rates, in layers which have had breakthrough, are not reflected in this method. There has been considerable controversy over the slug size necessary to maintain miscibility throughout the displacement process. In this method, the slug-size

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'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