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By T. B. Counselman

PRobably the earliest concentration of iron ore in this country was carried on in the northeastern magnetite areas. Magnetic concentration was relatively simple and gave a concentrate that, after agglomeration, and in spite of beillg high in phosphorus hecause of the dry concentrating methods then in use, was satisfactory blast-furnace feed. Production from the northeastern magnetitc area languished after the discovery and development of the Lake Superior ores, where there was seemingly an unlimited tonnage of high-grade ore, first the Michigan ores, and subsequently the still larger deposits of Minnesota. For years only the higher grade, direct shipping ores of the Lake superior district were mined. Those of Michigan, and of the Vermilion Range in Minnesota, were hard ores and came principally from underground mines. The softer ores of the Mesabi came partly from underground mincs, but mostly from the enormous deposits that could be worked by open-pit methods. The costs of ore from these open-pit deposits, even with the high initial cost of stripping, were so low that the underground mines of the Mesabi could hardly compete. The so-called Old Range ores, of Michigan and of the Vermilion Range of Minnesota, were hard and lumpy, and opened UP the burden in the blast furnace, therefore making possible harder driving with greater output. Also, some of these Ores were of such grade and physical characteristics that they were suitable for charge ore in the open hearth. These ores, therefore, commanded a price premium. and could compete with the softer, finer, but cheaper, Mesabi ores. The big tonnage reserves, however, are on the Mesabi. and it is these big open-pit deposits that contitue- our stock pile of iron ore, from which we are drawing so heavily during this war period. On the western end of the Mesabi the ore was found to be high in silica, and not suitable as furnace feed. As early as 1902, attempts were made to concentrate this so-called wash ore and by 1910 the first washing plant was put into operation. The Process was very simple, consisting essentially of a sizing and washing operation, with scalping screens, logwashers and tables, which later were replaced by classificrs. Ore particles finer than I00 mesh were deliberately wasted, because these fines were undesirable in the furnace. Fortunately, these tailings were impounded, and already are being reworked. Before long some of the low-grade ores began to require more elaborate treatment than the simple washing operation and, tables having been discarded because of their low capacity, in favor of classifiers, jigs were next introduced. These were able to discard coarser pieces of tailing than classifiers. Jigs are in active use today, various improvements having been made in their design and application. Various other machines and methods of concentration have been tried from time to time, and have in turn been discarded for more improved processes., The latest and most important process that has been 38

Jan 1, 1944

By F. D. Rosi, F. C. Perkins, L. L. Seigle

An investigation was made of the mechanism of plastic flow in coarse grained specimens of both sponge and iodide titanium at low (-196°C) and high (500° and 800°C) temperatures. Deformation by slip occurs predominantly on a {1011} plane and in a <1120> direction over this entire temperature range, and secondary slip on {101-1} planes becomes more prevalent with overthisentireincreasing temperature.range, The crystallographic habit of the predominant twin planes becomes more prevalent with type is temperature-dependent, and deformation by twinning increases as the temperature of testing is lowered. Kink bands were not observed at -196OC and rarely at the high temperatures. A LTHOUGH the deform a tional mechanisms in . -titanium at atmospheric temperature have been extensively investigated," there is little information regarding the influence of testing temperature on these mechanisms. The only available data come from the recent work by McHargue and Hammond, who extended single crystals of iodide titanium at a temperature of 815°C. No significant changes in the types of slip and twinning planes were observed, but increased activity on the type I, order 1 pyramidal slip planes and on the type 11, order 2 twinning planes was reported. These planes contribute very little to the deformation process at room temperature.&apos;&apos; &apos; Since there is interest in titanium as a material for use at both low and high temperatures, the present investigation was undertaken to examine the slip and twinning behavior in coarse grained specimens of titanium at -—196", 500°, and 800°C in order to determine the general effect of temperature on the mechanism of plastic deformation. Experimental Material Used and Specimen Preparation—Both sponge and iodide titanium were used in the present investigation; chemical analyses appear in Table I. These materials were arc-melted under argon into 25 g slugs, which were then cold-rolled approximately 90 pct to a sheet thickness of 0.05 in. Since the strain-anneal technique was used for obtaining coarse grains, the cold-rolled sheets were made into tensile specimens which were then annealed to produce a relatively coarse uniform grain structure prior to critical straining. The details of the strain-anneal treatment. size of grains, and the method for preparing the specimen surface for optical microscopy have been described in a previous report.&apos; In order to obtain a wider spread in crystal orientation for the present work, it was necessary to vary the rolling schedule to reduce the degree of preferred orientation in the annealed sheets prior to critical straining. Methods for Tensile Testing—The apparatus for experiments at the temperature of liquid nitrogen (—196°C) consisted of two concentric stainless steel

Jan 1, 1957

By D. A. Dukelow, K. Li, G. C. Smith

Decarburization in the Fe-C system by oxygen top blowing has been studied in laboratory -scale experiments. It is shown that equilibrium models fail to explain or predict either the course of refining or endpoint conditions, giving results which either are incompatible with the chemistry of the system or do not satisfy material balance requirements. Also the path of decarburization was found to vary even for heats made under apparently identica1 conditions. A promising approach to analyzing the decarburization results is to relate oxygen efficiency fm carbon removal to bath carbon content. This relationship for Fe-C heats shows the same range of oxygen efficiencies as is obtained in pilot-plant and commercial heats using hot metal-scrap charges. This implies that oxygen transfer is primarily controlled by the decarburization reaction itself, independent of other refining reactions. Therefore, it should be possible to study separately decarburization and slag-metal reactions. DECARBURIZATION is probably the most important reaction in steelmaking. Not only is it a main reaction in the refining of iron to steel but it also provides the stirring action in the bath necessary for the diffusion processes to proceed at reasonable rates so as to make a steelmaking process practical. Kinetics of decarburization in the open-hearth process has been a subject of investigation for many years.&apos;-B It is generally accepted that at steelmaking temperatures the rate of homogeneous C-0 reaction is extremely high and cannot constitute a rate-controlling step. Diffusion of oxygen through a boundary film in the metal phase has been suggested by arken&apos; as rate-determining. Recently, Larsen and sordah16 concluded from experiments in a laboratory furnace that, with oxygen supplied from air or combustion gases, the rate of "steady-state" carbon boil is controlled essentially by a diffusion process of O2, Co2, or H2O through a film of nitrogen above the slag surface. Displacing this diffusion film by a stream of nearly pure oxygen produced a ten-fold increase in the rate of carbon boil with the rates of slag-metal oxygen transfer, bubble nucle-ation, and other steps all apparently able to keep pace. In the top-blown basic oxygen process, however, the transport of oxygen takes a more direct route. and the state of bath agitation is much more turbulent than in the open-hearth process. In addition, direct contact of the gas with the metal phase provides opportunity for direct oxidation of carbon. It is likely that the rate-limiting factor for the decarburization reaction will be different. However, only a few descriptive discussions of the subject have been reported in the literature.10-l2 Studies of the decarburization kinetics based on plant or pilot-plant data are necessarily complicated and are influenced by other refining reactions which occur simultaneously. In order to investigate the mechanism of decarburization, experiments have been conducted in which carbon-saturated iron melts were top-blown with pure oxygen over a range of conditions. It is hoped that this study will form a foundation on which a more basic understanding of this important reaction may be built. EXPERIMENTS One group of blowing experiments was made in a standard 200-lb induction furnace and another group in a 500-lb induction furnace. The furnaces were modified to the general shape of a basic oxygen furnace by adding a rammed refractory cone section to the regular crucible body. Crucible and cone were of high MgO (95 pct) material. A water-cooled lance, 1/2 in. in diam and threaded at one end to take a nozzle, was used for blowing oxygen. The lance with its water and oxygen lines was supported on a cantilever arrangement so that it could be moved up, down, or sideways. Oxygen of 99.5 pct purity was supplied from a cylinder and metered through a rotameter equipped with pressure and temperature gages. Another pressure gage was located at the top of the lance. A schematic diagram of the assembly is shown in Fig. 1. Before each experiment, a weighed amount of ingot iron, containing 0.02 pct C, < 0.01 pct Si, 0.10 pct Mn, 0.019 pct P, and 0.015 pct S, was charged in the furnace and melted down by induction heating. Graphite was then added to the molten charge until it became saturated. When the temperature of the charge reached the desired level, the lance was lowered to a predetermined height above the bath

Jan 1, 1964

By J. E. Hanlon, S. R. Butler, R. J. Wasilewski

It is known that stoichiometric NiTi transforms to a structure of lower symmetry near room temperature. The present investigation deals primarily with the changes in the electrical and magnetic properties which occur at the transformation. The effects of composition and various heat treatments on electrical properties are also discussed. In recent investigations by Purdy and Parr,&apos; Wang et a1.,2 Dautovich and Purdy,~ Dautovich et a1.,4 and the authors, ~,&apos; NiTi has been observed to undergo a martensitic phase transformation from the ordered CsCl (B2) structure to one of lower symmetry. The crystal structure of the low-temperature modification is still not completely worked out. This transformation occurs near room temperature for the stoichiometric composition. The thermodynamic, elastic, crystallographic, and microstructural characteristics of this transformation for some compositions have been previously reported.&apos;-= In the present investigation, the changes in the electrical transport properties and magnetic susceptibility of NiTi when it undergoes the martensitic phase transformation have been measured. The approximate composition range covered is 48 to 52 pct Ti.* *All compositions are given in atomic percent._____________________ EXPERIMENTAL PROCEDURES AND RESULTS 1) Sample Preparation. The NiTi alloys were prepared from iodide titanium (>99.92 pct Ti) and vacuum-premelted carbonyl nickel (>99.95 pct Ni) by repeated arc melting under gettered argon and casting in a water-cooled copper mold. After the cast buttons were hot-forged at 800" to 950°C, the oxidized surface was removed by grinding and etching. Samples were cut from the worked polycrystalline buttons. After fabrication, the samples were annealed 1 hr at 900°C and water-quenched. The composition of the alloys was assumed to be the same as in the initial feed. This assumption was supported by material balance checks on 100-g arc-melted buttons which demonstrated quantitative recovery to within k0.02 pct. The oxygen content of the alloys was &apos;150 ppma (weight) and the carbon content was 30 to 50 ppm. 2) Electrical Resistivity and Hall Effect. The electrical resistivity was measured over the composition range 48 to 52 pct Ti for temperatures varying from 4.2"K to 900°C. The high-temperature and many of the low-temperature experiments were carried out using conventional 4-probe dc techniques.7 The Hall coefficient and ac resistivity were measured at 20 cps using the apparatus shown schematically in Fig. 1. The equipment is basically an ac potentiometer: The resistive or Hall voltage of the sample is balanced by a comparison voltage provided by a dividing network across a standard series resistance. The off-balance signal is amplified by a Tektronix 122 amplifier and detected by a Princeton Applied Research (PAR) phase-sensitive detector. The precision of the resistivity and Hall coefficient measurements is i0.1 and i3 pct, respectively. The uncertainty in the data is increased by i2 pct from the precision limits because of uncertainty in dimensions and possible end effects. The temperature dependence of the electrical resistivity and Hall effect for a stoichiometric (50.0 pct Ti) NiTi sample are illustrated in Fig. 2. Above 75"C, this sample has essentially the B2 structure, while below about 0°C it is completely in the low-tempera-

Jan 1, 1968

By D. Silverman, A. R. Brown

EquipmENT and methods for locating the points of entry of salt water into oil wells are described. These techniques make it possible to delineate accurately the top and bottom boundaries of water zones whether bottom water or intermediate zones of production, Data are given on tests by this survey method on a number of producing wells, Complete results were obtained on wells shelving water percentages ranging from high values to as Little as 10 pct salt water. A number of the wells tested were plugged back and the results are reported in detail. While not all the work-overs were successful, evidence, including the results of reruns by this survey method, points to failure of the plugback operations. The data provided in the tests discussed show, contrary to general opinion, that a large percentage approaching 50 pct of the wells showed intermediate water instead of bottom water. Furthermore, approximately a third of the wells tested showed multiple zones of water production. The equipment comprises a long pipelike assembly carrying 10 pairs of electrodes spaced apart a distance of 4 ft. A surface-controlled solenoid-operated switch is provided to connect each of the individual pairs of electrodes in turn to a single-conductor steel-armored cable by means of which the conductivity of the fluid in the vicinity of each of the electrode pairs can be continuously recorded at the surface. Any number of electrode pairs and any spacing can be used. This assembly is lowered on tubing and placed in position opposite the section of the well to be studied. A conventional rod pump is used to produce the well for the survey. The pump inlet is placed below the lowest electrode pair. The well is conditioned by pumping Out the salt water normally standing in the well and introducing fresh water into the annulus at the surface. When the resistivity of the water standing in the well has been increased to a sufficiently high value, the inflowing fresh water is stopped and the drawdown operation of the survey is started. As the fluid head is lowered by pumping, fluids flow into the well and the entry Of salt water is indicated by the change in resistivity of the fresh water opposite the &apos;Ones Of water entry, The process can be repeated as Often as necessary with little effort and without moving any well equipment to be sure that the fluids produced from each zone are representative Of the true reservoir content. Introduction The oil industry has been concerned from its inception with the control of fluids entering its wells. In order to effect the greatest economy of operation and to get the greatest total production of petroleum liquids out of the ground, the flow of gas and water must be controlled and often extensive workovers are planned and carried Out for this purpose. This has become even more important in recent Years because of the need for the conservation of natural resources. Whereas producing operations concerned with the original completion of a well are assisted to a great extent by a wide variety of instruments developed and perfected for that purpose, workover operations on oil wells have been greatly hindered by a lack of suitable instrumentation. The industry has searched for many years for a satisfactory instrument and process that

Jan 1, 1948

By P. R. Sperry, A. P. Beck

It has been shown1 that in poly-crystalline strips of high purity aluminum with a fairly random orientation distribution, grain growth progresses gradually until the average grain diameter reaches a value approximately equal to the strip thickness. Recent work at this laboratory led to the realization that grain growth might be impeded to a considerable extent in the presence of a sharply defined texture, where orientation differences between neighboring grains are small. In order to investigate this effect the following experiment was carried out with the same lot of high purity aluminum previously used for grain growth studies in randomly oriented material.&apos; Very large grain size was developed by grain growth at 650°C in specimens of 0.200 in. thickness. These specimens were then rolled to a thickness of 0.050 in. or 1.25 mm—a reduction of 75 pct. In the rolled strip each large grain corresponded to an elongated area easily identified by etching. After annealing for 1 to 25 min at 600°C and re-etching, these elongated areas were again recognizable. Within each area, corresponding to a single large grain before annealing, there formed by recrystallization a multitude of new grains with a fairly well developed preferred orientation. The orientation and the size of the new grains formed in areas corresponding to different large grains, varied widely depending on the orientation of the parent grains with respect to the rolling direction and the plane of rolling. Many areas were found where the average grain size was considerably smaller than the specimen thickness. Such an area occurred in a specimen cut in half before annealing. One half, containing a portion of the area in question, was annealed 1 min at 600°C, the other half, with the remaining portion of this area, for 25 min at the same tempera-Aluminum killed low carbon steel, § which is now used extensively for severe deep drawing or other difficult forming operations, is unusual in that its grain structure, after cold reduction and box annealing in accordance with conventional continuous sheet or strip mill practice, often is elongated, although at times it is equiaxed. Since this unusual structure has been found superior for many, but not all, severe forming operations, recrystallization of the steel, both at constant temperature and on continuous heating, was investigated and compared with that of rimmed steel in the hope that something might be learned about the mechanism of, and the factors controlling, the formation of such elongated grains. In this structure, the grains are elongated both in the lengthwise direction of the strip and transverse to this direction, even though nearly all of the extension in both hot and cold rolling is in the lengthwise direction. The grains are thus roughly pancake-shaped, being longer and wider than they are thick, as observed also by Burns and McCabe,1 and as illustrated by the typical structures shown in Fig 1. Fig la, representing a conventional longitudinal section, shows the length and thickness of the grains, whereas Fig Ib shows their length and width as seen by examining a section parallel to the sheet surface. Both illustrate the very irregular grain boundaries usually associated with the elongated grain shape. A finer equiaxed grain structure in this same grade is shown in Fig Ic. Either the elongated or the equiaxed structure may be present in the annealed product, and in rare instances the two types may coexist in a single specimen, as shown in Fig 1 d. Isothermal Recrystalliza-tion of Rimmed and Alamimum Killed Steel An aluminum killed steel known to have an elongated grain structure after conventional processing (Steel B, Table l), was selected for the initial recrystallization studies; for comparison, a rimmed steel, A in Table 1, was used. Samples of each in the form of hot rolled strip 0.075 and 0.095 in. thick, respectively, were cold rolled on a small laboratory mill in steps of about 0.010 in. per pass to obtain total reductions of 40 and 60 pct. Small pieces of the cold reduced strip were heated in lead at selected constant temperatures for one of several periods of time, then cooled in air. Rate of heating in the lead was, of course, very fast. Hardness of the cooled specimen was measured and a longitudinal section examined metallographically. Isothermal recrystallization curves for these two steels at 1050°F, based on hardness of the air cooled specimens, are shown in Fig 2 in which the amount of recrystallization corresponding to each plotted point is indicated. The marked difference in the behavior of these two types of steel is evident. After a corresponding amount of cold reduction, the rimmed steel recrys-tallizes in a much shorter time than the killed steel and the shape of its recrystallization curve, (plotted on a logarithmic time scale), is very different. The curve for rimmed steel indicates that recrystallization is analogous to isothermal transformation of aus-i.enite in that it proceeds at a progressively faster rate up to some 50 pct recrystallization, then at an increasingly slower rate. For the aluminum killed steel, however, the start of

Jan 1, 1950

By P. Ramachandrarao, T. R. Anantharaman

EVER since the technique of quenching metals and alloys from the melt (splat cooling) was perfected a decade ago, it has been recognized that the grain size of products solidified by this technique may be extremely small.&apos; The further observation that fcc metals quenched from the liquid state contain very few dislocations has led to the inference2 that metals are subjected to negligible or no stresses during the rapid solidification characteristic of the "gun" or "piston-and-anvil" technique. Evidence for the incidence of appreciable densities of stacking faults has, however, been obtained in case of some splat-cooled fcc and hcp alloys,3 although not for pure metals. In the light of these earlier observations it was considered desirable to study X-ray line-broadening effects, if any, in fcc metals rapidly cooled from the melt. In the present work pure silver (>99.99 pct), aluminum (>99.99 pct) and lead (>99.9 pct) were quenched from the liquid state from temperatures about 50°C above the melting point by the "gun technique" and the resulting foils were subjected to X-ray examination in a Philips Diffractometer. The quenched foils (up to -10 u thick) did not generally stick to the substrate surface and could be easily transferred to the Diffractometer without introducing any plastic deformation. The profiles of the first five reflections from the foils were recorded in each case with Cu Ka, radiation at the slowest available scanning speed of 1/8 deg per min. To correct for instrumental broadening, profiles were also recorded from the metals annealed in vacuo at suitable temperatures. The integral breadths of the X-ray reflections were arrived at by a procedure described earlier.&apos; There was a distinct suggestion of preferred orientation in the recorded intensities of reflections from aluminum and lead foils. Such an effect was not observed in case of silver. In addition, the integral breadths of X-ray reflections from splat-cooled aluminum and lead were not significantly different from those recorded for the annealed metals. The analysis was therefore continued only for silver where the X-ray line broadening was appreciable. The pure diffraction broadening, B, was evaluated for each X-ray reflection (hkl) from silver from the observed, B, and instrumental, b, breadths with the aid of each of the three equations due to Scherrer,5 Anantharaman and Christian,6 and Warren and Biscoe,7 respectively: Bs= B-b BAC=B- b2/B Table I gives the values of particle size, 71, the lattice strain, E, arrived at by the use of the following well-known relations and on the assumption that all observed diffraction broadening could be attributed to lattice strain or particle size, respectively: E = 1/4 cos ? n= B cos ? where A is the wavelength of X-radiation and 0 is the Bragg angle. As no significant peak shifts or asymmetry could be detected in the profiles from the foils, the possibility of any significant contribution due to twins or stacking faults was ruled out. The absence of faults is by no means surprising since pure silver is known to develop stacking faults only on severe deformation and the stacking fault densities recorded so far for even silver filings have been extremely low.&apos; The very low values for percentage mean deviation from the mean value for the particle size in Table I strongly suggest that all observed broadening in splat-cooled silver can be attributed only to small particle size. This conclusion receives further support from the lowest mean deviation recorded for data computed from the Scherrer equation based on Cauchy profiles that are considered characteristic of particle size broadening. Further analysis for separation of particle size and lattice strain effects was considered unnecessary in view of the very large mean deviations obtained for strain values and also the earlier results suggesting absence of even detectable strain in metals and alloys quenched from the melt. It is to be stressed in this connection that the particles are actually grains and not cells formed by walls of high dislocation density usually encountered in deformed samples. As such, the absence of strains is not surprising. The present results are probably the first to record X-ray line broadening due only to small particle

Jan 1, 1970

By H. C. Gatos, A. D. Kurtz

WITH the growing interest in the mechanism of self-diffusion of metals, the study of accurate and convenient methods for determining self-diffu-sion coefficients appears highly desirable. It was with this objective in mind that the present investigation was undertaken. Gatos and Azzam1 employed an autoradiographic technique for measuring self-diffusion coefficients of gold. This method involved sectioning of the specimen through the diffusion zone and recording the radioactivity directly on a photographic film. Because of the very short range of the emitted ß rays in gold, the activity recorded on the film was essentially the true surface activity. With proper choice of the sectioning angle, sufficient resolution could be obtained and the entire concentration-distance curve recorded in one measurement. For the boundary conditions of the experiment, where an infinitesimally thin layer of radioactive material diffuses in positive and negative directions into the end faces of a rod of infinite length, the solution of the diffusion equation is C/Cn = 1/v4pDt exp (-x2/4Dt) where C is the concentration of diffusing element (photographic density in this case), C,, is the constant (depending upon amount of radioactive material), x is the diffusion distance, D is the diffusion coefficient, and t is the time. Thus, by plotting the logarithm of the concentration vs the square of the diffusion distance, a straight line results and the slope contains the diffusion coefficient. In this manner, the self-diffusion coefficient of gold can be obtained as a function of temperature. In the present investigation the results reported by Gatos and Azzam1 have been verified, and the autoradiographic technique has been further developed and applied for the determination of the self-diffusion coefficient of gold at a number of temperatures. Furthermore, the energy of activation for the self-diffusion of gold has been conveniently determined. . Experimental Techniques Preparation of Specimens: The inert gold of high purity was received in the form of a rod from which cylinders were cut and machined to a diameter of 0.500 in. The specimens were annealed to a suitably large grain size and the faces were surface ground prior to the deposition of the radioactive layer. The radioactive isotope Au198 was chosen. It was produced in the Brookhaven pile by means of the reaction Au197 + n ? Au108. It decays by ß emission (0.96 mev) to Hg108 with the subsequent emission of a y ray (0.41 mev). 70Au 108 ? 80Hg 108 + -1e°. The half life of the Au108 is 2.7 days so that a strict time schedule had to be maintained in order to secure sufficient activity until the end of the experiments. For this reason, initial activities as high as 10,000 millicuries per gram were used. The gold arrived in the form of foil and was evaporated onto one face of each gold specimen cylinder to a thickness of about 100A. A sandwich-type specimen was formed by welding two such cylinders together. Evaporation of Gold: The gold was evaporated under vacuum from heated tantalum strips which were bent in such a way as to limit the solid angle through which the gold was allowed to vaporize, thus insuring a more efficient utilization of the gold. The specimens rested on flat brass rings which had an inner diameter of 0.475 in. The entire specimen-holding assembly could be manipulated from outside the vacuum system by means of a magnet which attracted a slug of soft iron attached to the assembly. By evaporating inert gold on glass slides under conditions identical to those employed for the radioactive gold, it was found that the thickness of the films was about 100A. Welding: The welding was performed by hot pressing in a stainless steel cylinder. The inside of the cylinder was threaded and fitted for two plugs. The specimens to be welded were placed in the middle of the cylinder and two pressing disks, one at each end, were inserted to avoid shearing stresses as the plugs were tightened. Mica disks were placed between the pressing disks and the specimens to prevent them from welding. The plugs were then tightened with a hand wrench and the entire unit was placed in an argon stream for about an hour to remove the oxygen. The unit was then inserted in the center of an argon atmosphere furnace maintained at about 700°C and left there for about an hour. Because of the difference in the temperature coefficient of expansion of the two metals, as the temperature rose. the pressure on the specimen-rollple increased and a weld resulted Welding was generally satisfactory under the conditions described.

Jan 1, 1955

By O. G. Kiel, G. W. Swift

The concept of "a continuous succession of steady-states", which has been applied successfully by Aromfsky and Jenkins to obtain a solution for the nonlinear partial differential equation describing the transient Darcy flow of gas through porous media, is demonstrated to be equally valid for transient non-Darcy flow. A mathematical model, which numerically solves the partial differential equation, is used to check the validity of the succession of steady-states solution. Comparison of sand-face pressure histories compelted by the two methods shows excellent agreement. The utility of the succession of steady-states solution in predicting performance of gas wells rests in the fact that no special computation equipment is required. The development of the succession of steady-states solution leads also to a practical method for determining and analyzing field test data. A method for taking gas-well test data under constant-rate conditions is presented. Experimental data obtained in the field by employing the constant-rate method are presented and analyzed in accordance with the succession of steady-states solution. Analysis of data in this fashion is demonstrated to give direct "in situ" information for reservoir permeability, porosity and turbulence or non-Darcy coefficient. INTRODUCTION The economics of gas production are dependent upon the transient behavior of flow within the reservoir. For production from a finite reservoir, the transient flow behavior can be subdivided into two parts. At first, the transient caused by the movement of the pressure "wave" into the reservoir is of importance. Later in the production history, the pressure-wave movement ceases and the second transient stage of material depletion becomes controlling. For reservoirs of relatively high permeability, it can be shown that the pressure wave moves into the reservoir and stabilizes quite rapidly. In the case of relatively impermeable reservoirs, quite the opposite is true. Although it is theoretically possible to compute the production capability of a well from the properties of the reservoir as determined by static tests and core analyses, more reliable information is obtained by conducting flow tests on the well and thereby obtaining some measure of "in situ" formation properties. For gas wells, there are two basic types of tests in existence: the flow-after-flow method,&apos; and the isochronal method.&apos; Both of these techniques are tailored to obtain data that can be analyzed in accordance with the empirical performance equation: In addition, the isochronal method makes provision for the sluggish nature of pressure-wave movement in "tight" formations by requiring pressure build-up between flows and by stipulating that data obtained on successive flows be analyzed at equal elapsed flow times. It can be demonstrated that either test is valid for reservoirs of high permeability. Further, since it has been pointed out that the pressure wave stabilizes rapidly for reservoirs of this type, tests of relatively short duration will give stabilized information on the performance of a well. Further decline of sand-face pressure and/or production rate may be determined by employing material-balance techniques. Cullender&apos; points out that for relatively impermeable reservoirs the flow-after-flow method gives invalid results. (See Appendix C.) If the isochronal method of testing is used, there are two alternatives: (1) the tests must be conducted for a sufficient length of time to obtain stabilized information (which may require months to accomplish); or (2) some method for extrapolating the results of short-term isochronal tests must be employed. The first alternative is impracticable because of manpower, conservation and economic considerations. Recourse to the second alternative requires some assurance regarding the reliability of the extrapolation technique. Poettmann and SchilsonJ present an empirical method for predicting stabilized performance. The present investigation was originally initiated to determine the reliability of this technique. To do this, a mathematical model was developed to simulate the Darcy and non-Darcy flow of gas through porous media. The model consisted of a finite-difference approximation of the nonlinear partial differential equation which was solved on an IBM 7090 computer. Long-term production histories were simulated by the model and compared against predictions obtained from the Poettmann-Schilson method. As the work progressed, it became apparent that a straightforward predictive equation could be developed by utilizing the concept of a succession of steady-states. As a result, the emphasis of the work was redirected to exploit the advantages of the new method.

By M. S. Azun

I do not at all agree with the basic points of the author&apos;s conclusion. The use of lognormal or normal model to respond to the attribute distribution function should be carefully questioned. If fitting a distribution function of regionalized variables is the main purpose, one may employ one of certain well-known families of distributions, such as Tukey&apos;s lambda functions. For instance, the distribution function of gold assay values studied by Krige (Krige, 1978) may fit the lognormal model well, but one should not exclude that the basic idea of using the distribution function of observed data is to have insight of the physical mechanism that gives rise to the regionalized variables. In Applied Geostatistics, there are many examples considering only lognormal or normal model for the distribution function of geostatistical data even if the observed distribution function has more than one mode. Of course, using lognormal or normal model always brings easy computation for the statistical properties of attribute under investigation. Still, I object to adopting any of those models without having any "statistical inference." As seen from the author&apos;s paper, lognormal and normal model produce the same average grade (0.746% copper) and almost the same sample variance. Therefore, which model explains the probabilistic behavior of ore deposit is always an important question that should be replied by the geostatistician using not the common sense but the statistical and probabilistic methods. For kriging procedures, such as linear kriging, one should describe either second order stationary properties or bivariate properties of regionalized variables. Second order properties, such as correlogram function or semivariogram function, are the inputs of the so-called kriging equations. Selecting one of any useable models for the observed second order properties, such as spherical model, is not easy since the models are not based on the correlations structure of the regionalized variables. How those models being used in Applied Geostatistics can be distinguished is another important problem. One may develop many fitting models to respond to the observed second order properties of regionalized variables. However, I suggest that the model should be based on the probabilistic behavior of geologic process. The author used spherical model for copper, wolfram, and silver grades from isotropic sector (Fig. 2, 4, 3b) and exponential model for silver grades obtained along raises in isotropic sector (Fig. 3a). It seems that those semivariograms given in Fig. 3b for isotropic sector and Fig. 4 may be described by the random model implying that regionalized variables do belong to renewal process (Azun, 1983). If I knew the total number of data points used in estimation, may prove that my conclusion is correct. Recalling the test for the first order sample correlogram value, the test procedure is introduced such that the independence is rejected if [Ir(1) I > Za/2 N1/2] where Za/2 is the a/2 percentile of standard normal random variable and N is the total number of samples used in estimation (Azun, 1983). For the other observed semivariogram functions I suggest the author might try to use the so-called "Markovian model" describing not only the correlation structure of regionalized variables, but also the physical mechanism that produces the regionalized variables. The Markovian model for correlogram function is, [p (h) = T 1ih , h>1 ,] The Markovian model for the other second order properties of ReV are also derived. [T veß], in the above equation, show, for example, structural change and mineralizational variation in a considered deposit, respectively (Azun, 1983). In selecting any model, it is not easy to search for the "best" response to the observed second order properties of ReV&apos;s. The Markovian model, based on a theoretical understanding of underlying mechanism, gives more information about the occurrence of regionalized variables and respond to all properties. Random model and the so-called hole effect structure can be easily defined as a special form of the Markovian model (Azun, 1983). An estimation of any second order properties of regionalized variables may be computed through (N-1) lag. However, the dependency between the regionalized variables may be deemed to have "died out" after the so-called stationarity width (range). In practice, the estimation is carried out through 25% of the total number samples available. Therefore, the large fluctuations around the zero level and variance for correlogram or covariogram function and semivariogram function, respectively, cannot be observed. Since the number of pairs involved in the estimation of higher second order properties is small, the estimation variance at those lags is large. There is no need to show higher order estimated second order properties. After using one of any kriging procedure for block estimation, the distribution function of average grades has the same mean as the drilling sample grades but

Jan 1, 1986

By John F. Elliott, Robert D. Pehlke

The rate of reaction of nitrogen with liquid iron and with binary alloys of iron and Al, Cb, Cr, Ni, O, S, Si, and W were measured. The surface active elements, oxygen and sulfur, decrease the rate markedly. The other alloying elements have very little effect on the rate except when they function as deoxidizers, The rates of absorption and de-sorption were found to be equal. Several possible reaction mechanisms which may control the rate are considered. In order to describe completely the behavior of nitrogen in steelmaking processes, the mechanisms of mass transfer between the gaseous and liquid phases, nitrogen and iron, respectively, must be understood. A kinetic study to determine the nature of these mass transfer processes was undertaken, and the results of that investigation are presented in this paper. Specifically, the study was directed toward determining the influence of alloying elements on the rates at which pure nitrogen gas at constant pressure is absorbed and desorbed by liquid iron solutions: A previous paper1 reported measurements of the equilibrium solubility of nitrogen in liquid binary iron alloys. The experimental data are presented and discussed first and then several possible rate limiting mechanisms are considered. PREVIOUS RESEARCH The results of several investigations on the rate of absorption of nitrogen by liquid iron and iron alloys have been reported.2-14 There is little agreement on the rate coefficients among these studies because of the influence of geometry on the experimental system and of the purity of the liquid iron. The rate was found to be influenced by alloying content for the binary liquid iron systems: Fe-Al,2 Fe-C,4,6 Fe-Cr,4,5,8 Fe-Mn,5 Fe-Ni,5,8 Fe-O,9,10 Fe-O,9,10 and Fe-Si.2,6,7,11 Several investigators12"15 have reported that the rate of nitrogen absorption is increased in a reducing gas mixture and decreased in an oxidizing atmosphere. A mechanism for the retardation by oxygen of the absorption of nitrogen has been described by Naeser18 as the formation of an iron oxide film at the gas-metal interface. The film slows the absorption rate until it disolves in the metal, thus permitting nitrogen to enter the liquid iron. Karwat17 discussed the influence of oxygen in terms of the formation of gaseous molecules of nitrous oxide which represent a higher energy form than the nitrogen and oxygen or the oxidizing gas and consequently constitute an energy barrier for the process. Fischer and Hoffmann10 showed that the oxygen markedly reduces the rate of absorption of nitrogen, the rate constant being one order of magnitude smaller in liquid iron containing 0.15 to 0.24 pct 0 as compared to that in melts containing 0.001 to 0.02 pct 0. Although Chipman and Murphy2 reported that the rate of absorption of nitrogen in liquid iron was essentially independent of temperature, Eklund3 found that the rate increases strongly with increasing temperature as did Kootz4 and Saito.5,6 Karnaukhov and Morozov7 also reported a large temperature coefficient, but related it to increased stirring at higher power inputs in an inductively heated system. All of the authors above have treated their results assuming that the reaction is diffusion controlled, that the surface reaction is in equilibrium with nitrogen gas, and that a "first order" reaction takes place. Karnaukhov and Morozov7 and Humbert; who studied the rate of absorption in a closed system by observing pressure changes in the system as a function of time, concluded that their results best fit a diffusion-type analysis. This was further verified by von Bogdandy, Dick, and stranski18 and Fischer and Hoffmann10 who found the initial rate of

Jan 1, 1963

By Marshall Pease, R. J. Brandon

A UTILITY that has a large consumption of coal must insure an adequate and sound supply of fuel. The Detroit Edison Co., which has an annual coal consumption of about four million tons and spends approximately $32 million a year for coal, including freight charges, has developed a program for fuel procurement and for evaluation and selection of fuel for reliable and efficient plant operation. Fuel Procurement Coal Purchasing Division: The Fuel Supply Div. of the Purchasing Dept. combines all of the procurement functions in one group, which must maintain adequate stocks of fuel. In addition to its usual purchasing duties, the division also governs transportation, follow-up, invoice and freight bill, in cooperation with the Accounting Dept. The Fuel Div. is comprised of the fuel agent, an assistant fuel agent, a coal buyer and five coal clerks, who follow the movement of each car, initially approve freight bills and invoices, and file claims whenever there is a shortage of one ton or more. The fuel agent reports directly to the purchasing agent of the Company, and all major programs are planned jointly with the chief purchasing officer. The apparent individuality of the fuel section is necessary because of the tremendous volume of coal cars handled each day, sometimes as many as 500, which must be handled promptly to complete the fastest possible move from the mines to the plants. Determining Annual Coal Volume: Through the combined studies of a Production Dept. Load Committee and the Controller&apos;s office, accurate predictions of coal requirements for any given year are provided the Fuel Dept. from 12 to 15 months in advance. This is divided into the requirements of all individual power plants and central heating plants. This in turn determines the quantity and quality for plants whose specific fuels vary with the type of equipment installed. In the Detroit area, which has a high industrial load, early estimates of annual coal consumption usually are resolved at the end of the year within 4 or 5 pct of the original plan. Operating in a highly developed industrial area eases the task of estimating primary output; and, with the residential demands increasing in a steady and fairly well-defined pattern, the overall coal schedules are not subject to radical changes during any given year. Selecting Suppliers: At any time, but especially during or before an emergency, the coal supply factor must be made secure. This is particularly true in the procurement of utility fuel. There are always extreme quantities of so-called "bargain" coal available during the buyers&apos; markets, such as recently prevailed. These opportunistic offerings may be considered a means of averaging down overall price, rather than as a steady and dependable supply source. Coal is purchased on contract from mine operators and sales agents who have proved reliable. They are not opportunists who desert for higher dollars in times of duress; they do not fail to fulfill contracts when markets rise or overship when markets dip. The progressive operator today who is willing to expend capital to improve quality and service deserves much more consideration than a matching of short-term pennies. When a company has a high volume of annual needs, all phases of the mine supply must be considered. The mine must be able to produce the quality required at a fair price and be able to sell oversizes of coal in enough volume to screen sufficient nut and slack. It must crush coal and sell mine run at prices in line with competitive nut and slack and be willing to do so when there is no demand for prepared sizes. Determining Price: The public utility is in direct competition with any of its customers who can, if savings are guaranteed, generate their own power. Today, to a greater extent than ever before, private industry must do a better overall job than Government-controlled operations. The price of coal must be realistically balanced with the price paid by almost all industries and the railroads as well. The supply-demand ratio in coal is not difficult to discern. There is access at all times to Govern-

Jan 1, 1952

By W. C. Winegard, W. J. Bratina

Internal friction characteristics and temperature dependence of the torsion modulus for iodide zirconium containing 2.4 pct Hf were investigated, using a low frequency pendulum technique. The internal friction curve consists of a background which increases as the temperature increases, a maximum at 860°C apparently a background due to the al-lotropic transformation, a maximum due to grain boundary relaxation with an associated heat of activation of 58,000 cal per mol, and an anomaly below 350°C which may be associated with a precipitation perphenomenon, Oxygen in below small amounts reduces the grain boundary maximum substantially. The variation of the torsion modulus at 20°C was found to be 3450 Kg per mm2 for the zirconium used in the present work. IT is well known that small amounts of certain solutes materially affect the ductility of zirconium. Lely and Hamburger,&apos; as early as 1914, found that high purity zirconium exhibited a remarkable ductility, while Fast&apos; has shown that oxygen and nitrogen can cause substantia1 embrittlement. Treco" has recently demonstrated that the ductility decreases sharply with the oxygen content, and that 2 atomic pct O2 embrittles zirconium to such an extent that cold working is impossible. The marked decrease in ductility is difficult to understand in view of the fact that Domagala and McPherson4 report the solid solubility of oxygen in zirconium to be 29 atomic pct at 500 °C. Another metal which behaves much the same as zirconium in this respect is titanium. Pratt et al." investigated the internal friction characteristics of titanium and the effect of oxygen on the internal friction values. It is evident that internal friction measurements are of value for studying grain boundary segregation, as shown by Pratt et al. for oxygen in titanium, by Pearson for oxygen in copper, and by Maringer and Schwope for oxygen in molybdenum. With this in view, the internal friction characteristics of zirconium and the qualitative effect of oxygen on the grain boundary relaxation phenomenon were investigated. Materials and Experimental Procedure The zirconium used in the present work was supplied by the Foote Mineral Co. in the form of wire 0.05 in. diam. The analysis supplied by the manufacturer indicates the amount of hafnium as 2.4 pct, less than 0.01 pct O less than 0.01 pct N,, less than 0.02 pct H,, and less than 0.001 pct C. Additional spectro-graphic analysis indicates the other main impurities as follows: 0.01 pct Fe, 0.05 pct Si, 0.008 pct Cu, <0.005 pct W, <0.001 pct Al, <0.05 pct Mg, <0.001 pct Ni, <0.02 pct Ca, and <0.01 pct Ti. Microscopic examination of the material in the as received condition revealed very fine grains with numerous twins. Specimens were annealed either in situ in the internal friction apparatus or in evacuated silica tubes in an auxiliary furnace. When the specimens were annealed in the auxiliary furnace, they were wrapped in identical zirconium wire to prevent contamination by the container. Metallographic sections were taken in all cases. Some were taken from the specimens used for internal friction measurements after completion of the experiments, while others were taken from control specimens at intermediate stages of the experiments. lnternal friction values were obtained by measuring the free decay of a low frequency torsion pendulum (1 cycle per sec), the suspension of which was

Jan 1, 1957

By J. J. Gilman

The data presented indicate that the critical shear stress and strain-hardening Thedatapresentedrate of a zinc monocrystal depend on the orientation of its slip direction with respect to its external boundaries. The tendency of a crystal to form deformation bands also depends on its shape. THE plastic behavior of pairs of zinc monocrystals in which both members of the respective pairs had the same orientation with respect to the longitudinal axis, but each had different orientations with respect to their rectangular external shapes, were compared in this investigation. The purpose of the investigation was to see what influence the shape or surface of a zinc crystal has on its mechanical properties. In a previous investigation of triangular zinc monocrystals,1 anomalous axial twisting was observed which seemed to be related to the triangular shape of the crystals. Wolff,&apos; in 400°C tensile tests of rectangular rock-salt crystals bounded by cubic cleavage planes, found that, of the four equivalent slip systems, the two with the "shorter" slip directions yielded and produced slip lines at lower stresses than the other two. This observation and the work of Dommerich³ as formulated by Smekal4 as a "new slip condition" for rock-salt: "among two or more slip systems permitted by the shear stress law, with reference to the formation of visible slip lines by large individual glides, that slip system is preferred which has the shortest effective slip direction." More recently, Wu and Smoluchowski5 reported essentially the same effect for ribbon-like (20x2x0.2 mm) aluminum crystals at room temperature. Experimental Chemically pure zinc (99.999 pct Zn), purchased from the New Jersey Zinc Co., was the raw material. Glass envelopes, containing graphite molds and zinc, were evacuated while hot enough to outgas the graphite but not melt the zinc. At a vacuum of about 0.2 micron the envelopes were sealed off and then lowered through a furnace at 1 in. per hr so as to melt and resolidify the zinc and produce mono-crystals. One-half of one of the molds is shown in Fig. la. Each mold consisted of four pieces from a cylindrical graphite rod that was split longitudinally and transversely at its midpoints. Rectangular milled grooves 0.050 in. deep and % in. wide formed the mold cavity when the split halves were assembled with twisted wires. Fig. lb shows the specimen shape obtained when the top and bottom mold-halves were rotated 90" with respect to each other. Good fits prevented leakage and excess zinc was necessary to provide enough liquid head to fill the mold completely. In removing soft crystals from the molds it was impossible to avoid small amounts of bending. However, manipulations were carried out whenever possible with the crystals protected by grooved brass blocks. All specimens were annealed prior to testing. From the top and bottom sections of each crystal, X-ray specimens and tensile specimens 7 to 8 cm long were sawed. The tensile specimens were annealed inside evacuated tubes for 1 hr at 375°C. Next the crystals were cleaned and polished by 2-min dips in a solution of 22 pct chromic acid, 74 pct water, 2.5 pct sulphuric acid, and 1.5 pct glacial acetic acid.&apos; Cleaning was followed by a 10-sec dip in a 10 pct caustic solution, then washed in water and alcohol, and dried. This treatment results in a bright surface covered by an invisible oxide film. The testing grips were a slotted type with set screws and were supported in a V-block during the mounting operations in order to avoid bending the crystals. A schematic diagram of the recording tensile-testing machine is shown in Fig. 2. The machine has been described elsewhere.&apos; The head speed was 0.3 mm per sec for all tests. The crystal orientations were determined by the Greninger X-ray back-reflection method with an estimated accuracy of 1. Description of Crystal Geometry A schematic picture of a rectangular zinc mono-crystal is shown in Fig. 3. ABD designates the front edge of a basal plane (0001) of the crystal, the only active slip plane for zinc at room temperature. Of the three possible (2110) slip directions, the active one is indicated by an arrow. Cartesian coordinates are taken parallel to the specimen edges. The normal, n, to the basal plane (n is parallel to the hexagonal axis) has the direction cosines a, ß and ?. X0 = 90 — y is the angle between the longitudinal axis and

Jan 1, 1954

By H. S. Price, J. E. Warren

Techniques for studying the performance characteristics of heterogeneous reservoirs have been developed. The effect of permeability variation on both the steady-state and the transient flow of a single fluid has been investigated. Limited comparisons with field and laboratory data have been made. The physical models studied consist of random three-dimensional arrays of homogeneous porous blocks. The permeabilities of the individual elements are assigned according to a specific distribution function; uniform anisotropy is introduced by varying the relative dimensions of the blocks. A particular model is perturbed simply by re-arranging its elements at random. The behavior of a physical model is determined by digitally solving its numerical analogue. Based on computational experiments, subject to the restrictions implied by the assumptions that were made, the following general conclusions have been drawn. 1. The most probable behavior of a heterogeneous system approaches that of a homogeneous system with a permeability equal to the geometric mean of the individual permeabilities. 2. The effects of flow geometry and anisotropy on the most probable value of the effective permeability of a heterogeneous medium are finite but not significant. 3. The permeability determined from a pressure build-up curve lor a heterogeneous reservoir gives a reasonable value for the effective permeability of the drainage area. 4. A qualitative measure of the degree of heterogeneity and its spatial configuration are obtained from a comparative study of core analysis and pressure build-up data. It has been indicated that these conclusions are predicated on the assumption that the core analysis and the pressure build-up data represent true reservoir characteristics. Common sources of error in these data have been discussed. One of the most significant problems of reservoir engineering is that of determining the nature and the disposition of the heterogeneities that inevitably occur in petroliferous formations. It is with this problem that this paper is concerned. Extensive research, both theoretical and experimental, has provided reasonable descriptions of the physical processes that are associated with primary and secondaryrecovery mechanisms. Similar progress in the fie1d of numerical analysis and the evolution of truly high-speed digital computers have made it feasible to calculate the behavior of these mechanisms under almost any environmental conditions. It appears to be logical, then, to conclude that the mechanistic performance of any reservoir can be predicted with some confidence. Unfortunate1y, a necessary condition for the validity of this conclusion is that the formation be adequately described in a macroscopic sense. This condition cannot be satisfied ill general; therefore, a frustrating situation currently exists — it is possible to compute the effect of reservoir heterogeneity on behavior, but it is not possible to specify the heterogeneity itself. In many cases, the predicted behavior of a project is so completely dominated by irregularities in the formation&apos;s physical properties that the gratuitous assumptior, of a particular form for the variation can reduce the solution of the problem to a mere tautological exercise. While all porous media are microscopically heterogeneous, only macroscopic fluctuations need be considered since the fundamental concepts of reservoir mechanics are based on macroscopic quantities. For the simplest case in which only one physical property varies from point to point, the degree of heterogeneity that is apparent depends on three distinct factors, i.e., the nature of the property&apos;s variation (frequency distribution), its disposition (spatial distribution) and the inherent stability of the mechanism being studied. Consequently, any attempt to devise an unambiguous scale of heterogeneity must take these factors into account. Since this investigation is intended to be exploratory, it will be restricted to single-phase flow because of the simplification implied; both steady-state and unsteady-state behavior will be considered. Furthermore, to keep the number of parameters

By T. B. Counselman

PRobably the earliest concentration of iron ore in this country was carried on in the northeastern magnetite areas. Magnetic concentration was relatively simple and gave a concentrate that, after agglomeration, and in spite of beillg high in phosphorus hecause of the dry concentrating methods then in use, was satisfactory blast-furnace feed. Production from the northeastern magnetitc area languished after the discovery and development of the Lake Superior ores, where there was seemingly an unlimited tonnage of high-grade ore, first the Michigan ores, and subsequently the still larger deposits of Minnesota. For years only the higher grade, direct shipping ores of the Lake superior district were mined. Those of Michigan, and of the Vermilion Range in Minnesota, were hard ores and came principally from underground mines. The softer ores of the Mesabi came partly from underground mincs, but mostly from the enormous deposits that could be worked by open-pit methods. The costs of ore from these open-pit deposits, even with the high initial cost of stripping, were so low that the underground mines of the Mesabi could hardly compete. The so-called Old Range ores, of Michigan and of the Vermilion Range of Minnesota, were hard and lumpy, and opened UP the burden in the blast furnace, therefore making possible harder driving with greater output. Also, some of these Ores were of such grade and physical characteristics that they were suitable for charge ore in the open hearth. These ores, therefore, commanded a price premium. and could compete with the softer, finer, but cheaper, Mesabi ores. The big tonnage reserves, however, are on the Mesabi. and it is these big open-pit deposits that contitue- our stock pile of iron ore, from which we are drawing so heavily during this war period. On the western end of the Mesabi the ore was found to be high in silica, and not suitable as furnace feed. As early as 1902, attempts were made to concentrate this so-called wash ore and by 1910 the first washing plant was put into operation. The Process was very simple, consisting essentially of a sizing and washing operation, with scalping screens, logwashers and tables, which later were replaced by classificrs. Ore particles finer than I00 mesh were deliberately wasted, because these fines were undesirable in the furnace. Fortunately, these tailings were impounded, and already are being reworked. Before long some of the low-grade ores began to require more elaborate treatment than the simple washing operation and, tables having been discarded because of their low capacity, in favor of classifiers, jigs were next introduced. These were able to discard coarser pieces of tailing than classifiers. Jigs are in active use today, various improvements having been made in their design and application. Various other machines and methods of concentration have been tried from time to time, and have in turn been discarded for more improved processes., The latest and most important process that has been 38

Jan 1, 1944

By W. M. Phillips

Processing kaolin clays from the sedimentary deposits of Georgia and South Carolina is described in this article. While the major processing steps are touched on briefly, emphasis is given to the dewater-ing of the clay-water slurries (slips) formed in the processing of kaolin clays. The dewatering steps discussed include gravity settling, centrifugal dewatering, vacuum filtration and thermal drying. Particular attention is given to vacuum filtration and the variables affecting filtration of these kaolin clays. Kaolin consists essentially of the mineral kaolinite, which is a hydrated aluminum silicate (Al2O3 . 2SiO,). Commercial deposits of kaolin occur in several areas of the U. S., but approximately 90% of the kaolin produced in this country comes from Georgia and South Carolina. These deposits are of sedimentary nature and occur in a geological fall line in the Tuscaloosa formation at elevations between 300 and 450 ft above sea level. Over two million tons of kaolin clays are used by industry in the U. S. each year. A big percentage of this tonnage is used in the paper industry for coatings in making glossy and high quality grades of printing papers. In addition, large tonnages are used as pigments; as fillers for rubber, plastic and fertilizers; and in ceramics. Properties of kaolin that make it widely used in the above applications are its particle size fineness, natural whiteness, chemical stability and non-abrasiveness. In addition to these desirable properties, it is relatively inexpensive. The finer coating grades of clays range in price from $15 to $28 per ton while the coarser filler grades sell within a range of $7 to $13.50 per ton. Pure kaolin particles are small hexagonal flat platelets. Above the 2-p size, the particles usually consist of stacks of plates, while below the 2-p particle size they occur as individual flat, hexagonal plates. Since these individual platelet particles provide the most desirable coating and flow characteristics, major importance is given to particle size fractions of 2 p and smaller. Generally, coating grade clays are those with all particles smaller than 15 p and at least 70% of the particles less than 2p. These coating grades also have 50% or more of the particles smaller than 1 µ in size. The extremely fine grades of coating clay currently being produced approach the range of 100% smaller than 2p. The filler grades of kaolin have 100% of the particles passing 325 mesh but have less than 70% of their particles below the 2-p range. Fig. 1 is a schematic representation of the major processing steps involved in preparing kaolin clays for marketing. MINING All kaolin mining is open pit. The ratio of overburden to clay will average 3:1, but this ratio can, of course, be much higher depending upon the grade of the clay and the size of the deposit. Most of the commercially mineable deposits occur from 20 to 120 ft below the ground surface. Both draglines and pans are used in removing the overburden and mining the clay deposit itself. After mining, the most common method of transporting the clay to the processing plant is by blunging or re pulp-

Jan 1, 1963

By Thomas E. Garnar

Zirconium and hafnium are curious elements because they are almost always found together in nature. Zirconium was discovered by Klaproth in 1789 and isolated 35 years later by Berzelius. Because hafnium&apos;s chemical properties are so close to those of zirconium, it was not discovered until 1923 when Coster and Von-Heresey detected it using x-ray spectrographic analysis. These elements occur most commonly in nature as the mineral zircon (ZrSiO4) and less commonly as the oxide baddeleyite (ZrO2). They also are found as a variety of other silicates. Zircon was identified as a component in alluvial and beach sands in 1895, but it was not produced in any quantity until 20 years later. Zircon is always a coproduct from TiO2 mining and processing. During World War I it was produced as a coproduct of beach sand mining for titanium minerals just south of Jacksonville Beach, FL, and was patented as a refractory. It was not until the 1930s when Zircon Rutile, Ltd. began mining at Byron Bay on the east coast of Australia that zircon was first used as a foundry sand. Later in the 1940s, NL Industries, Humphreys Gold Corp., and E. I. du Pont de Nemours & Co., Inc. began production of zircon sands from fossil beaches in northeast and northcentral Florida. Baddeleyite first became available as a commercial product in 1916, but never in the quantity of zircon. Zircon holds a unique position as an industrial mineral because it is used for both its physical and chemical properties as well as an ore of zirconium and hafnium metals. Australia is the major zircon producer followed by South Africa and the US. Zircon is also produced in India, Sierra Leone, Sri Lanka, Malaysia, China, Thailand, and Brazil. Undeveloped heavy mineral beach sand reserves containing zircon are known to occur in Egypt, Malawi, Senegal, and Tanzania. Locations are shown in Fig. 1. Mineralogy Zirconium and hafnium are always present together in naturally occurring compounds. Most commonly they form as the silicate sometimes containing iron, calcium, sodium, manganese, and other elements. Less commonly they are found as oxides in combination with titanium, thorium, calcium, and iron. Zircon is the most common form. It is extremely resistant to weathering, therefore, often it is present in ancient beach sands and placer deposits. Although resistant to alteration from external sources, it is vulnerable to internal alteration as the result of thorium and uranium substituting for zirconium either in the zircon lattice or in solid solution. Alteration to the metamict state takes place as radioactive emanations from these elements disorder the crystal lattice, accompanied by hydration, reduction in specific gravity, and changes in color. The mineralogy of zircon and baddeleyite and variation of physical and chemical properties are shown in Table 1. The effects of zircon&apos;s internal alteration and darkened color can be corrected by heating to 1000°C for 30 min or so. A certain time-temperature relationship makes it possible for decolorization and reordering of the crystal lattice to take place when heating at higher temperatures for shorter periods or at lower temperatures for longer periods. After heating, x-ray diffraction patterns are sharper, the grains may be harder, and except for particles of malacon, the grains will be white or colorless in the absence of grain surface coatings. The color change is only temporary and the particles slowly darken with time. Zircon fluoresces light yellow in shortwave ultraviolet light. If exposed to ultraviolet light for extended periods of time, white (calcined) zircon turns purple. With time the induced color begins to fade and eventually disappears (e.g., calcined Florida zircon exposed to ultraviolet light for 24 hr still retains faint, but discernible, purple color after six months).

Jan 1, 1983

By M. N. Dunlap

Tries article summarizes the successful incorporation of a flash-flooding stream into the tailing-disposal system at the St. Joseph Lead Company&apos;s Federal Division mill, in St. Francois County, Missouri. The mill was built in 1906, by the Federal Lead Co., as its No. 3 mill for the concentration of southeastern Missouri lead ores, and damming Davis Creek was first considered in 1908. Plans were made also in 1925 and in 1937. Dam layouts varied from a reinforced concrete structure to a barrier built of tailings alone. All were abandoned because of liability that would be incurred by flashflood rupturing of an incompleted dam. By 1942 mill capacity had reached 12,000 tons daily and increasing tailing-disposal costs again focused attention on the Davis Creek basin. This time the problem of riskless dam building was solved. Moreover, most of the items that appeared in the answer were materials that normally required wasting and the major portion of labor involved performed functions that it would normally have done, without constructive benefit, elsewhere. The new layout also made possible advantageous changes in mill-water supply pumping; static head being reduced from 514 ft to 95 ft, friction head from 4900 ft to 2860 ft, and pumping can be done now at periods of low power demand. The following facts about the Davis Creek watershed explain the 36-year reluctance to reach these, and other, benefits. Size: 3600 acres. Outline: roughly pear-shaped, 2 1/2 by 3 miles at the largest dimensions. Topography: mostly hill land with steep valleys. Relief : 760 minimum to 1153 maximum. Maximum rainfall: 3.36 in. per hour. Permanent water: none natural. Now 2200 gpm discharged through 16-in. drill hole from mine pumps underground. Geology: the 17 acres near dam centerline is Bonne Terre dolomite covered with sand and gravel eroded from Pleistocene beds that cap some of the hills. The remainder of the pond basin is on Davis shale. Soil cover: mostly second-growth timber with some abandoned fields; all subject to careless burning, which reduces water-retaining ability. Flood history: flash-flooding that had taken at least one life. Downstream values: two railroad bridges before creek intersection with Flat River. Immediately below confluence, a highway bridge, a low-water crossing, a few business establishments and several blocks of residences. In July 1942 the following segments of an ingenious plan were put into operation. A ditch 270 ft long, 16 ft wide and 5 1/2 ft deep was excavated to bedrock in the gravelly soil along the proposed dam&apos;s centerline. This excavation, which exposed many gravel-filled channels, was run full of slimes drawn from a riser set in the top of an adjacent tailings-disposal

Jan 1, 1947

By D. M. Boulin, E. S. Greiner

Single crystals of vanadium were bent at 293" and 77°K to a maximum fiber strain of about 1 pct. Analysis of slip line and etch markings of- crystals deformed at either temperature show the slip planes are {112}. The slip directions at 298° and 77°K, deterwined from the asterism axes of rotation of crystals compressed in a {110} direclion, were (111). Etch pits, associated with dislocations, were observed in the plastically deformed vanadium. There was no evidence of mechanical twinning. THIS paper presents results on single crystals of vanadium plastically deformed by bending and compressing at 298° and 77°K. Bcc metals have been observed to slip on {110}, (1121, and (123) planes while the slip direction has invariably been found to be ( 111) 1 Lindley and smallman2 have studied the deformation intension of polycrystalline vanadium between 298° and 20°K and reported that at and above 77°K the deformation is predominantly by slip, but at 20°K the deformation is associated with twinning. Later, Edington and smallman3 found that single crystals of vanadium compressed in a (111) direction at 77°K deformed by twinning on { 112}( 111) systems. Clough and pavlovic4 have reported that mechanical twins were observed in vanadium loaded by impact at 77°, 173°, and 195°K, respectively. PREPARATION OF SINGLE CRYSTALS The vanadium single crystals were made from commercial vanadium reported to contain 0.03 pct C, 0.03 pct 0, 0.02 pct N, 0.0X* pct Ca, 0.0X pct Si, proximately 0.8 cm diam, 4 cm long and were grown in (100) and (110) directions. A crystal for studies of etch pits was gound to have a face parallel to a {l00} plane by the Bond crystal-orienting technique.7 In order to avoid straining, the crystals were placed on the steel mount with a low-melting organic compound (glycol phthalate) before grinding. Crystals for the bending experiments were ground to have the four side faces parallel to ( 100) planes. The crystals were electropolished8 in 10 pct H2So4 using a current density of about 3 amp per sq cm to remove the strained surface material. The crystals were bent slowly by three-point loading in a stainless-steel jig designed by Sylwestrowicz.9 The end rollers of the jig were 3.8 cm apart. DEFORMATION AT 298°K The bent vanadium crystal, after removal from the jig, had a radius of curvature of 20.4 cm over the 2-cm length close to the center loading roller, where the maximum bending moment occurred. This radius of curvature corresponded to a maximum fiber strain of 0.9 pet. The side faces contained slip bands as shown in Fig. 1. These bands are straight where the strain is high, top and bottom of micrograph, but are curved on either side of the neutral axis in the center. This curvature of the slip bands in the low-stress area may be due to cross slip. The plastically deformed crystal was subsequently electropolished and then electroetched in 10 pct H2SO4 solution, using a current density of 0.25 amp per sq cm. The structure is shown in Fig. 2. The directions of the traces on two adjoining faces were plotted stereo graphically, Fig. 3.* Since there were two sets of

Jan 1, 1968