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By Nathaniel Arbiter

THE separation of minerals by flotation can be regarded as a rate process, with the extraction of any one mineral determined by its flotation rate, and the grade of concentrate by the relative rates for all the minerals. So regarded, the significant variables for the process are those that control the rates. These variables are of two types, the first describing the ore and its physical and chemical treatment prior to flotation and the second characterizing the separation process in the cells. This paper will examine the variation in rates for a group of separations, will show that a simple rate law appears to govern, and will consider the relation of the control variables to the rates. The use of rate constants for evaluation of performance and efficiency will be discussed. Flotation involves the selective levitation of mineral and its transfer from cell to launder. The flotation rate is the rate of this transfer. It may be defined by the slope of a recovery-time curve for any cell in a bank, or at any time in batch operation. The objective in flotation rate study is an equation expressing the rate in terms of some measurable property of the pulp. This can be either the concentration of floatable mineral in weight per unit volume1,2 or a relative concentration, which will be a function of the recovery." A rate equation for an actual flotation pulp will contain at least two constants, both to be determined from the data. One of these, the initial concentration or proportion of floatable mineral, is not necessarily equal to the feed assay because of nonfloatable oversize or locked particles." The other, a rate constant, is a measure of proportionality between the rate and the pulp property on which the rate depends. The value of the rate constant will be determined by the values of all variables which control the process and will be changed by significant changes in any of them. It is, therefore, a direct measure of performance. Where recovery or grade change continuously with flotation time, the rate constant will be independent of time and will characterize the entire course of the separation. Development of Rate Equations Rate equations can be developed either by analysis of the mechanism of the process or by direct fitting of equations to recovery-time data. Sutherland's attempt by the first method' suggests that the effect of particle size variation on the rate complicates the derivation of a simple equation applicable to an ore pulp. A further problem with an ore is the concentrate grade requirement, which usually involves a variable rate of froth removal. Thus the final rate for any cell may depend on the froth character and froth height, as well as on the pulp composition. This does not imply that each cell cannot reach a steady state2 in which the rate will depend ultimately on pulp composition. The second method is the fitting of rate equations consistent with the necessary boundary conditions* to experimental recovery-time curves. On the assumption that under constant operating conditions the flotation rate is proportional to the actual or relative concentration of floatable mineral in the pulp, a generalized rate equation may be expressed as follows: Rate = Kcn [I] where K is the rate constant, c is some measure of the quantity of floatable mineral in the pulp at time t, and n is a positive number. In previous rate studies, the value of n has been taken as 1, either by direct assumption," or as a result of the hypothesis that bubble-particle collision is rate determining.' A first order equation results, which after integration in terms of cumulative recovery R, leads to Loge A/A-R = Kt [2] The quantity A is the maximum possible recovery with prolonged time under the conditions used. No conclusive proof for the validity of this equation in flotation has been advanced. The evidence cited in its support consists entirely in the demonstration that it appears to apply to a limited number of recovery-time curves."' It will be shown subsequently that this procedure is not sufficient to establish the order of a flotation rate equation. The possibility that the equation may be of higher order therefore requires examination. If, in particular, the exponent in eq 1 is assumed to be 2, then after integration there results R = A2Kt/1 + AKt [3] with K again a rate constant and A the maximum proportion of recoverable mineral. Eq 3 may be

Jan 1, 1952

By W. C. Smith, P. J. Hickey

After a short historical background of the process evolution, this article descvibes present-day plant facilities and operating techniques utilized for high-purity bismuth production. The plant is one of the world's largest, with an annual output of some one million pounds of refined bismutlz. PREVIOUS papers1 written by staff members of Cerro de Pasco Corp. have referred briefly to the production of refined bismuth. Since the Corporation is one of the world's foremost producers of high-purity bismuth, a detailed description of the process for extracting the metal may be of general interest. Following a short historical background of the development of the actual process, this presentation will trace the progress of bismuth from its entry into the primary smelting circuits to its concentration in electrolytic lead cell slimes. Our facilities for the treatment of anode muds will be described and the extractive methods given in some detail, with particular emphasis on the techniques which result in the production of refined metal. HISTORICAL BACKGROUND Shortly after Cerro de Pasco began smelting operations at Oroya, Peru in 1922, it became apparent that the dust carried by copper converter gas contained appreciable amounts of bismuth. Although dust collection efficiency was poor prior to building of the 550-ft stack and installation of the central cottrells in 1938, a large stock of dust was accumulated during the intervening years, having the following approximate composition: Oz. per ton Ag - 11.0 Pct Sn — 0.5 Pct Pb - 49.0 Pct Zn - 6.5 Pct Bi - 2.0 Pct Insol. - 1.5 Pct Cu - 0.7 Pct Fe - 2.3 Pct Sb - 3.0 Pct S - 10.0 Pct As - 7.5 In the mid-1920's, experimental crucible melts of this dust with carbon indicated that most of the bismuth and silver, and some of the lead, could be reduced to a fairly clean bullion. Other products were a small amount of leady copper matte and a slag high in zinc, arsenic, antimony, and lead; this slag contained some tin but only small quantities of silver, bismuth, and copper. After the laboratory results had been confirmed by operation of a small reverberatory, a dust reduction furnace was constructed. The ±10 pct Bi-Pb bullion produced from this operation was stocked until 1930, when an Oroya-designed converter type furnace3 was installed for the elimination of arsenic, antimony, and some lead from the bullion. This process concentrated the bismuth from 10 to about 60 pct. By means of the bismuth process developed4 by W. C. Smith at East Chicago (1909-1914) and the discovery of a method5 for separation of lead from bismuth with chlorine gas in 1929, it became possible to begin production of refined bismuth. Unfortunately, bismuth deleaded with chlorine always contained residual chlorides, and the removal of the chlorides by caustic soda left a lead content of 0.02 to 0.04 pct. This final problem was solved6 by substitution of air-blowing for the caustic treatment, which effectively removed all excess chlorine and gave bismuth which was practically lead-free. In 1934, a pilot electrolytic lead refinery began operations at Oroya. Lead smelting was resumed in 1935 and two years later a 100-ton-per-day lead refinery was put into service. In conjunction with the latter, the present-day Anode Residue Plant was constructed. Until 1940, the plant treated both lead anode slimes and dust reduction bullion. The dust reduction furnace was shut down in that year, and all cottrell dusts (with the exception of the product from the arsenic cottrell) were mixed with pyrite and treated in a Wedge roaster to eliminate all possible arsenic. Calcine from this operation joined the sinter plant feed; hence the bismuth from the copper and lead circuits was collected in the lead bullion and subsequently in lead anode slimes from the electrolytic lead refinery. The latter source has been the only bismuth-bearing material of any consequence entering the Anode Residue Plant from late 1940 to the present. A copper refinery began operating in 1948, and the cell mud from this plant is mixed with lead slimes and processed through the same circuit, though only a small quantity of bismuth is present in electrolytic copper cell residues. BISMUTH INTAKE Present-day routes which are followed by the new bismuth feed from its entry into the primary smelting circuits to its arrival at the Anode Residue Plant are traced schematically in Fig. 1. As illus-

Jan 1, 1962

By J. U. Messenger

A technique is described whereby the resistance of an emudian to breaking can be quantitatively determined. Produced ailfield emulsions are usually the water-in-oil type and, accordingly, do not conduct an electrical current. However, there is a threshold of A-C voltage pressure above which an emulsion will break and current will flow. The more stable an emulsion, the higher the required voltage. A Fann Emulsion Tester, modified so that low voltages (0 to 10 v) can be accurately measured, is suitable. This technique has application in evaluating the effect of a demuksifier on the stability of an emulsion. Emulsions can, in essence, be titrated with demulsifiers by adding a quuntity of demulsifier, stirring, and measuring the voltage required to cause current to flow. Any synergistic effect of two or more materials added simultaneously can be followed accurately. A demulsifier that significantly lowers the threshold voltage (from 100 to 400 v to 0 to 10 v for the emulsions in this study) is effective and can cause the enlulsion to break. A demulsifier that will bring about this drop in the threshold voltage at low concentration ir very desirable. The technique is also well adapted for rapidly screening demulsifiers. INTRODUCTION Stable emulsions in produced reservoir fluids resulting from certain well stimulation and completion procedures are common problems. The use of suitable demulsifiers can often mitigate these difficulties. At the present time, a rapid and efficient method for selecting satisfactory demulsifiers is not available. It is badly needed. Reliance is now placed primarily on trial-and-error procedures. A new test method has been developed which permits a more rapid and precise selection of demulsifiers. It involves measuring the electrical stability potential of an emulsion before and after a demulsifier has been added. This paper describes this method and shows where it should have application in field emulsion problems. NATURE OF OILFIELD EMULSIONS Two immiscible components must be present for an emuhion to form; we are concerned here with crude oil and water. An emulsifier must be present for tin emulsion to be stable. J Emulsifiers can be substances which are soluble in oil and /or mter and which lower interfacial tension. They can be colloidal solids such as bentonite, carbon, graphite, or asphalt which collect at the interface and are preferentially wet by one of these phases. Unrefined crude oils can contain both types of emulsifiers, A popular theory is that, of the two phases in an emulsion, the dispersed phase will be the one contributing most to the interfacial tension.' Usually this phase contains the least amount of emulsifier. The stability of a water-in-oil emulsion is affected by the fol1owing: l) viscosity; (2) particle or droplet size; (3) interfacial tension between the phases; (4) phase-volume ratios; and (5) the difference in density between the phases. A stable emulsion is usually characterized by high-viscosity, small droplets, low interfacial tensions, small differences in density between its phases, and slow separatian of the phases. It also has low conductivity (high electrical stability potential). Water-in-oil and oil-in-water emulsions"' are both common; however, oil field emulsions are predominantly water-in-oil emulsions. The emulsions which commonly occur during oompletion and stimulation operations contain a combination of several of the following: acids, fracturing fluids (oil, water, acid), and formation water and oil. Produced emulsions usually contain formation water and oil. Emulsions form in oil wells because oil and water are mixed together at a high rate of shear in the presence of a naturally occurring or unavoidably produced emulsifier. During the completion and stimulation of productive zones, and while formation fluids are being produced, oil and water are very often commingled. These mixtures are formed into emulsions by agitation which occurs when the fluids are pumped from the surface into the matrix of the formation or produced through the formation to the surface. Restrictions to flow (such as perforations, pumps, and chokes)".'" increase the level of agitation; tight emulsions are more likely to form under these conditions. Often an emulsified droplet is an emulsion itself.'" Therefore, emulsion-breaking problems can be quite complex. The complexity can be even greater if a third phase (gas) is included. Demulsifiers operate by tending to reverse the form of the emulsion. During this process, droplets of water become bigger, viscosity is lowered, color becomes darker, separation of the phases faster and electrical stability potential approaches zero. Any of these effects could be followed as a means of determining emulsion stability. However, electrical stability potential is the most reproducible and most easily measured parameter for following the stability of a water-in-oil emulsion.

Jan 1, 1966

By M. Kaitz

A continuing discussion in both the petroleum engineering and economic literature is directed to the difficulties encountered in the use of discounted cash flow rate of return (DCF) as a measure of investment worth. Although useful in most Instances, DCF has been criticized because it is time-consuming in its trial-and-error solution, theoretically invalid, not adaptable to cash flow streams yielding multiple return solutions and not entirely reliable in selecting between mutually exclusive investments. The theoretical invalidity of DCF stems from the reinvestment assumption implicit in the calculation that earnings are reinvested at the DCF rate. The emerging consensus of the economic literature is that the net present value or the present worth of the net cash flow stream (discounting at the average opportunity or cost of capital rate) is more correct and reliable. Other criteria proposed have been ratios of net present value divided by initial investment or by present value of all investments in a project. All of these criteria are simple to determine and explicitly assume a reinvestment rate for [he income generated by a project. This paper develops and discusses a theoretically valid profitability criterion which is simple to compute and retains the appeal of a percent return on investment. It is called "percentage gain on investment" or PGI. It measures the gain an investment is expected to realize over like capital invested in the average opportunity and explicitly considers reinvestment potential. Why add another Concept to the large array of investment criteria now available, any one of which, or perhaps a combination of several, appears to embrace the form's (or individuals) objectives? The answer is that not one of the existing criteria provides both a readily comprehensible and theoretically valid measure of risk coverage that has general application. The proposed PGI does fulfill these requirements. INTRODUCTION An ancient expression warns that "one must yield to the times" — there are better ways of doing things. A review of the petroleum engineering and economic literature on one topic alone, measurement of investment worth, certainly is witness to this truth. In use for a number of years, the DCF has recently received attention, directed mainly to its theoretical invalidity. Several alternatives to DCF have been proposed to provide a valid, simply determined criterion to describe investment worth and to overcome the criticisms previously mentioned. This paper introduces another method called percentage gain on investment (PGI) and is proposed as but one of several yardsticks that should be used in making investment decisions. MEASURES OF INVESTMENT WORTH This paper will consider only those criteria which give weight to the time pattern of future earnings. These criteria are usually compared with an average opportunity rate or cost of capital of the firm to judge the relative worth of the investment. For purposes of demonstration, a 9 percent average opportunity rate will be used throughout this paper. Implicit in the DCF calculation is the assumption that earnings are reinvested at the DCF rate. Some argue, though, that there is no reinvestment assumption,' that the DCF rate is simply that maximum rate of interest one can pay on the investment over the life of the project and break even. The determination of DCF is accomplished by discounting the net cash flow stream at that rate (DCF) which will yield zero. The question is: why should reinvestment potential be explicitly considered in calculating return on investment or other criteria measuring economic worth? Perhaps the answer lies in consistent or equal treatment of future cash flow. It appears entirely illogical to give different present worth value to $1 received, say, 10 years from now, which is the circumstance resulting in comparing projects with different DCF returns. In fact, $1 received in 10 years has the same value regardless of which project generated the income. DCF return thus favors investment projects which are expected to provide early income as compared to those providing long-term income. Not surprisingly, the controversy on reinvestment assumption is an old one. Hoskold' discussed this same problem in 1877. He considered the future income from mineral properties as an annuity or a series of fixed future payments. (As will be demonstrated, his equation can be modified for variable income.) Prior to Hoskold, the value or what one could pay for the mine, was determined with the use of standard, single-interest tables. Here is what Hoskold said with regard to these tables. "This table, and others of its kind, to be found in most works on annuities, is constructed correctly according to

By Allan E. Martin, Harold M. Feder, Irving Johnson

The cadmium-uranium system was studied by thermal, metallographic, X-7-ay and sampling techniques; special emphasis was placed on the establishment of the liquidus lines, The single inter metallic phase, identified as the compound UCd11 melts peritectically at 473°C to form a-umnium and melt containing 2.5 wt pct uranium. The cadmium-rich eutectic (0.07 wt pct uranium) freezes at 320.6°C. Solid solubilities in uraizium and cadmium appear to be negligible. Between 473°C and 600°C the liquidus line is retograde. NO publication relating to the cadmium-uranium phase diagram was found in the literature. The establishment of this diagram was of considerable interest to us because of a possible application of the system to the pyrometallurgical reprocessing of nuclear fuels. Analysis of liquid samples, metallographic examination, thermal analysis, and X-ray diffraction analysis were used to establish the phase diagram from about 300° to 670°C. Particular emphasis was placed on the establishment of the liquidus lines. The same system was concurrently studied in this laboratory by the galvanic cell method.' Both studies benefited from a continual interchange of information. MATERIALS AND EXPERIMENTAL PROCEDURES Stick cadmium (99.95 pct Cd, American Smelting and Refining Co.) contained 140 ppm lead as the major impurity. Reactor grade uranium (99.9 pct U, National Lead Co.) was most often used in the form of 20-meshspheres. This form was particularly suitable because it does not oxidize as readily as finer powder. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The liquid sampling technique is described elsewhere2 alumina crucibles (Morganite Triangle RR), tantalum stirring rods, tantalum thermocouple protecthecadmiumtion tubes, Vycor or Pyrex sampling tubes, and grades 60 or 80 porous graphite filters were used. Uranium dissolves in liquid cadmium rather slowly. In order to achieve saturation of the melts it was necessary to modify the procedure of Ref. 2 by the use of more vigorous stirring and longer holding periods (at least 3 hr) at each sampling temperature. The samples were analyzed for uranium by spectro-photometry (dibenzoyl methane method) or by polar- ography. The analyses are estimated to be accurate to 2 pct. Thermal analysis was performed on alloys contained in Morganite alumina crucibles in helium atmospheres. Standard techniques were employed; heating and cooling rates were about 1°C per min. For the determination of the peritectic temperature, Cd-10 pct U charges were first held for at least 50 hr at temperatures in the range 435° to 460°C to form substantial amounts of the intermediate phase. For the determination of the effect of cadmium on the a-p transformation temperature of uranium, charges of Cd-25 pct U (-140+100 mesh uranium spheres) were first held near the transformation temperature, with stirring, to promote solution of cadmium in the solid uranium. The holding times and temperatures for these treatments were 18 hr at 680°C for the cooling run and 28 hr at 630°C for the heating run. Alloy specimens for X-ray diffraction and metallographic examination of the intermediate phase were prepared in sealed, helium-filled Vycor or Pyrex tubes. Ingots from solubility runs and thermal analysis experiments also were examined metallographically. Crystals of the intermediate phase were recovered from certain cadmium-rich alloys by selective dissolution of the matrix in 20 pct ammonium nitrate solution at room temperature. Temperatures were measured with calibrated Pt/Pt-10 pct Rh thermocouples to an estimated accuracy of 0.3°C. However, the depression of the freezing point of cadmium at the eutectic is estimated to be accurate to 0.05°C because a special calibration of the thermocouple was made in place in the equipment with pure cadmium just prior to the measurement. EXPERIMENTAL RESULTS The results of this study were used to construct the cadmium-uranium phase diagram shown in Fig. 1. This diagram is relatively simple; it is characterized by a single intermediate phase, 6 (UCd11), which decomposes peritectically, and which forms a eutectic system with cadmium. The solid solubilities in the terminal phases appear to be negligible. An unusual feature of the diagram is the retrograde slope of the liquidus line above the peritectic temperature. The Liquidus Lines. The liquidus lines above and below the peritectic temperature are based on three separate solubility experiments. The data are shown in Fig. 1 and are given in Table I. It is apparent from the figure that the solubility data obtained by the approach to saturation from higher temperatures fall on substantially the same lines as those obtained

Jan 1, 1962

By R. E. Morgan, D. L. Douglass

The determination of phase relationships and solid-solubility limits can be performed by quantitative metallography in addition to the usual X-ray and metallographic techniques. For example, Beck and smith1 redetermined the ß/ß + ?, ß + ?/?, a/a + ß and a + ß/ß boundaries in the Cu-Zn system by measuring the volume fraction of second phase of several alloys and extrapolating the volume fraction-composition curves to 0 and 100 pct. A modification of this technique is suggested for certain alloy systems, in which it is not necessary to use several alloy compositions but merely one. A single two-phase alloy may be used to determine terminal solubilities in the following manner. The method consists of equilibrating samples of the alloy in a two-phase region adjacent to the desired solid solution, at three or more temperatures, quenching, measuring the volume fraction of second phase present, and applying an analytical treatment to calculate the unknown solid solution. However, two restrictions are inherent in this technique. They are: 1) only certain types of alloy systems are amenable to it, and 2) the general features of the system must be known. The first drawback to the new technique, i.e., that only certain types of systems may be studied, necessitates that the composition at one end of the tieline must either be constant with temperature or well established as a function of temperature. Either a pure metal or some intermetallic compounds fulfill the former. If it is assumed that the volume per gram-atom of a dilute solution is unchanged by the addition of element B to element A, the composition of the solid solution in equilibrium with the second phase may be determined by a material balance and is given by where X, = volume fraction of B in a solid solution Xc = volume fraction of B in compound c X = volume fraction of B in alloy f = volume fraction of second phase The composition by weight may then be determined by the use of tables in the Metals Handbook2 when the density ratio of the solid solution constituents is known. A possible alternative treatment involving the use of the lever rule is less precise than the above tech- nique. This may be used when the density of the solid solution is either known or may be calculated from X-ray data for several compositions. The following analysis is then made. The ratio of compound to solid solution (by weight) may be expressed as follows: x0 - x wc = xr-x = x0 - x r2i Xc -X where Wc = weight of compound w = weight of solid solution x, - alloy composition, weight percent x = unknown composition Xe = compound composition but where V, = volume of compound VA = volume of solid solution pc = density of compound p, = density of solid solution fc = volume fraction of compound fB = volume fraction of solid solution and fs = l -fc then If pc and xc are known, and f, is measured, then pB is the only unknown on the right side of Eq. [4]. The known densities of the solid solution can be plotted for various compositions and can then be expressed mathematically as a function of composition. The use of an expression of pB = f(x)reduces the equation to one unknown—the desired solubility. In the event that the densities are unknown, they may be calculated for various compositions from Vegard&apos;s law. The calculated values are then plotted and expressed analytically. The most accurate results are obtained for Eq. [4] when fc<< 1, i.c., when (x, -x,) - 0, &/l-f, - m; but as fc/l -fc - 0, (xl-x,)- (x, - x), and x - x,,. However, the accuracy with which fc can be measured decreases as f, decreases.3 Alloys for investigation must be selected by a compromise, which is based upon an error analysis of Eq. [4] and knowledge of the accuracy of volume fraction measurements. An examination of phase diagrams in the literature showed many which were amenable to the technique described here. The zirconium-copper system was selected in order to determine the solubility of copper in beta zirconium. Pieces of an alloy which was arc-melted three times were wrapped in tantalum foil and sealed under an argon atmosphere in Vycor tubes. The sealed samples were equilibrated at temperatures from 850" to 960°C for 3 weeks and quenched to room temperature by smashing the capsule in water. Several planes of polish were examined, and

Jan 1, 1960

By P. H. Lindon, J. C. Billington

Fe-O melts containing 0.045 pct 0 were deoxidized with Mn-Si-A1 alloys. Product compositions were reluted to the melt and alloy compositions and were found to be most sensitive to the aluminum content of the alloy. Low residual oxygen contents could be obtained when aluminum oxide was present in the Products because of the reduction of silica and manganese oxide activities. Flotation of the Products from a quiescent melt was followed both by analysis of the oxygen content and metallographic measurement of inclusion concentration. MnO-SiO2-A12O3 products were found to float most rapidly when their composition was such that their viscosity may be expected to be low. Changes in the particle size distribution indicates that particle coalescence occurred and differences in the degree of coalescence are thought to be responsible for the different flotation rates observed between products 0f differing composition. Measured flotation rates were slower than those Predicted from a model based on Stoke&apos;s Law, although alumina flotation might be reasonably accounted for by this model. Interfacial effects between oxide particles and the melt are believed to be responsible for the discrepancy. It has been recognized that deoxidation products constitute a large proportion of the nonmetallic inclusions present in killed steel. The amount of oxide inclusions which originate as deoxidation products depends largely upon three factors. These may be summarized, according to P16ckinger1 as: 1) Amount of primary products remaining in the steel prior to cooling. 2) Residual dissolved oxygen content of the steel after deoxidation. 3) Amount of secondary products, formed during cooling and solidification, which remain entrapped in the solid steel. In a well-deoxidized steel containing residual aluminum and/or silicon, the equilibrium dissolved oxygen content is usually very low and so the maximum amount of oxide which may be produced as secondary deoxidation products is small in comparison with the amount of primary products. It may be seen, therefore, that the amount of indigenous nonmetallic inclusions may be minimized if a low dissolved oxygen content is achieved by deoxidation and if the primary deoxidation products are efficiently removed. Oxides which originate by reaction of the metal stream with the atmosphere during teeming are not considered in the present study. It is known that two or more deoxidizers may result in a lower equilibrium oxygen content when used in conjunction with one another than when any of the individual deoxidizers are used alone. Equilibrium studies by Hilty and crafts2 and by Bell3 have shown that manganese increases the effectiveness of silicon as a deoxidizer, and Walsh and Ramachandran4 relate this to a reduction in the activity of silica in the products as the manganese :silicon ratio in the steel increases. It was also shown by Herty&apos;s work on deoxidation of steel by silico manganese alloys,5 that there existed an optimum ratio of manganese to silicon which gave a minimum inclusion content. This ratio was in the range 4:l to 7:l and the (FeO-MnO-SiO2) products formed by such deoxidation practice were found to lie in a composition range having very low liquidus temperatures (1170 to 1250°C approx). The optimum manganese:silicon ratio was then explained by postulating that these fluid products were able to coalesce and that the larger particles formed floated out of the steel very quickly as predicted by Stoke&apos;s Law. The present work examines the effectiveness of various Mn-Si-A1 alloys as deoxidizers and their effects on the composition and removal of primary deoxidation products from a quiescent melt. EXPERIMENTAL TECHNIQUE Approximately 250 g of prepared Fe-O alloy, containing 0.045 to 0.055 pct O, were melted in an alumina crucible and deoxidized at 1550°C by plunging a thin steel cartridge containing the deoxidizer below the melt surface. A high frequency induction furnace supplying current at 8.5 kHz was used to heat a graphite susceptor, the interior of which had been machined to give a wall thickness of 0.85 in. to form a receptacle for the alumina crucible. The iron melt was essentially quiescent as the induced current was concentrated at the external surface of the graphite susceptor by the skin effect. A nonoxidizing atmosphere was maintained over the melt by passing a continuous stream of argon through the lid of the susceptor. The melt temperature was measured before deoxidation, and again at the end of an experiment by means

Jan 1, 1970

By R. F. Nielsen, D. E. Menzie

The object of this study was to determine if crude oil could be produced successfully by a process of crude oil vaporization using carbon dioxide repressuring. This process appears to have application to highly fractured formations where the major oil content of the reservoir is contained in the non-fractured porosity with little associated permeability. Crude oil was introduced into the windowed cell and carbon dioxide was charged to the cell at the desired pressure. A vapor space was formed above the oil, and the crude oil-carbon dioxide mixture was allowed to come to equilibrium. The vapor phase was removed and the vaporized oil collected as condensate. Samples of all produced and unproduced fluids were analyzed. Tests were also performed to evaluate the amount of vaporized oil that can he produced by rocking from a high to a lower pressure. The carbon dioxide repressuring process was applied to a sand-filled cell to investigate the performance in a porous medium. A test was performed to evaluate how the condensate recovery changes as the size of the gas cap in contact with the oil changes. INTRODUCTION This study has been directed toward a relatively new process of vaporization of crude oil designed to increase ultimate production of hydrocarbons through the application of carbon dioxide to an oil reservoir. Suggested advantages of carbon dioxide repressuring of a petroleum reservoir are: (1) reduction in viscosity of liquid hydrocarbons due to the solubility of carbon dioxide in crude oil, (2) swelling of the reservoir oil into a larger liquid-oil volume with a resulting increase in production and decrease in residual oil saturation due to an increase in the relative permeability to oil, (3) displacement of more stock-tank oil from the reservoir since the residual liquid is a swelled crude oil, and (4) gasification of some of the hydrocarbons into a carbon dioxide-hydrocarbon vapor mixture. Balanced against these advantages are several detrimental factors which must be evaluated; i.e., high compression costs and corrosion of well equipment and flow lines. Some of the more outstanding contributions to the study of carbon dioxide injection have been reviewed in order to furnish a basis for a continuation of research pertaining to this method. The literature reviewed1-8 has been limited to that dealing with carbon dioxide repressuring processes or with carbon dioxide-crude oil-natural gas phase behavior. Articles relating to carbonated water injection and literature published on the use of low pressure carbon dioxide gas injection in water flooding have not been included in this study. In 1941 Pirson5 suggested the high pressure injection of carbon dioxide into a partially depleted reservoir for the purpose of causing the reservoir oil to vaporize and thus produce the oil as a vapor along with the carbon dioxide gas. By reducing the pressure on this produced mixture of hydrocarbons and carbon dioxide at the surface, it was proposed to separate the hydrocarbons from the carrier gas. He theorized that essentially all the oil in a reservoir could be produced by simply injecting enough carbon dioxide to vaporize the residual oil. This present investigation deals with the vaporization of a crude oil by carbon dioxide, the molecular weight and gravity of the vaporized oil product and the characteristics of the residual oil after several repressuring cycles with carbon dioxide. An attempt is made to evaluate the merits of a vaporization process for the crude oil rather than a flow process where the oil recovery is determined by relative permeability considerations. Such a vaporization of crude oil by carbon dioxide repressuring appears to have possible use in a highly fractured formation where the major oil content of the reservoir is contained in the non-fractured porosity with little permeability. The carbon dioxide flows into the fractures, contacts the crude oil in the matrix and vaporizes part of the crude oil; this vaporized oil is produced and recovered and the carbon dioxide is reinjected again. The specific problem of this study is to attempt to answer this question; Can crude oil be produced successfully (technically, but without economic considerations) from a petroleum reservoir by a process of vaporization of the crude oil by carbon dioxide repressuring? DEFINITION OF TERMS AS APPLIED IN THIS STUDY Carbon Dioxide Contact: One cycle in which carbon dioxide was injected and bled off. Condensate: The hydrocarbon liquid which was condensed out of the mixture of hydrocarbon-carbon dioxide vapor upon reduction of the pressure of the vapor. Hydrocarbons Produced (HCP): All the hydrocarbon!, which were vaporized by the carbon dioxide repressuring process and were removed from the cell during any specific cycle or carbon dioxide contact. Hydrocarbons Unproduced (HCU): All the hydrocarbons which were not vaporized by the carbon dioxide

By P. D. Zemany, G. W. Sear, B. W. Roberts

Vanadium metal is embrittled by hydrogen at a temperature as low as 250°C when held in the presence of manganese metal and water vapor in a rough vacuum. It is established that the property changes are caused by the catalytic decomposition of water vapor at the vanadium surface and the diffusion into and solution in the vanadium of the resultant hydrogen. It is found that manganese is a necessary component of the catalyst. The manganese is transported in the vapor phase by an unknown molecule. A deuterium tracer experiment demonstates the role of water vapor in the embrittle-ment process. VANADIUM metal foils were observed to become embrittled&apos; at a temperature of about 300 °C when held in the presence of manganese metal and a small amount of moist air, This paper describes the investigation to find the embrittling agent and an understanding of the relatively low temperature reactions that are involved. Experimental The vanadium metal foil used was prepared by cold-rolling and pack-rolling 32 mil sheet" in a series of steps down to 1 mil foil. The original observation was confirmed by sealing vanadium foils of 3 x 10 sq cm into individual Pyrex tubes with manganese powder† and a con- trol tube containing only the vanadium foil. These tubes were evacuated to 10 -5 mm Hg without baking and sealed. After heat treatment for 200 hr at 300°C, the control foil showed no change in duetility, whereas the foil contained in the manganese— containing tube was embrittled. The visual appearance of each was unchanged. A series of Pyrex sample tubes, about 2.5 cm diam and 25 cm long, were prepared, each containing a 3 x 10 sq cm piece of foil and 5 g manganese powder at the lower end of the tube. By reducing the time of anneal and the temperature of these samples, it was found that embrittlement could be created at 250°C in a time as short as 1 hr. Since the vanadium metal used here has been drastically cold-worked by rolling, it is assumed that it contains a maximum number of dislocations. To check the possible necessity of dislocations in this low temperature reaction, a vanadium foil sample was annealed in Vycor for 2 hr at 800°C to re crystallize and reduce the dislocation concentration. Metallographic examination showed grains which were not visible before annealing. The embrittlement procedure was carried out at 300°C and 3 hr. Upon checking the foil no embrittlement was observed. Further experiments demonstrated that about 6 hr at 300°C are required to create embrittlement in the foil. This delay in the onset of embrittlement in the vanadium foil suggests but does not prove that dislocation channels play a role in the embrittlement phenomena. If manganese metal is necessary for this low temperature embrittlement, do other elements in the transition metals group yield the same result? To check this qualitatively, a group of elements of similar atomic radii were obtained and sealed as before into Pyrex tubes with a sheet of vanadium foil. These tubes were annealed at 250°C for 6 hr and included (with radii)-2 A1 (1.4A), As (1.25A), Be (1.2A), Co (1.25A), Cr (1.45A), Cu (1.25A), Fe (1.25A), Ga (1.2A), Ge (1.25L%), Mn (1.3A), Ni (1.25A), Si (1.2A), Ti (1.45A), Zn (1.3A), air, H,O, 10 cm Hg of dry hydrogen, and MnO, powder. Upon testing the above sample foils for brittleness, only the manganese-containing tube yielded a brittle foil. Manganese Transport—To eliminate contact of manganese metal powder and vanadium foil, sample tubes were prepared with fritted glass barriers. The embrittlement reaction was still found to occur. Thus, the mode of transfer of manganese is certainly vapor transport. A vanadium foil was embrittled by this mechanism in an evacuated Pyrex tube for 8 hr at 300°C. By means of X-ray fluorescence analysis,&apos; the amount of manganese added to the surface was established at 5 ±2 x 10 -6 g per sq cm. Since the average rate of manganese deposition is known, an effective average pressure of an assumed carrier compound can be computed. ___ P = M/T v2p mkT

Jan 1, 1959

By J. S. Levine, M. Prats

A homogeneous and uniform cylindrical reservoir containing oil and gas is fractured vertically on completion and is produced at a constant bottom-hole pressure. The fracture has an infinite flow capacity, is of limited lateral extent and is bounded above and below by the impermeable strata defining the vertical extent of the reservoir. Results show that such a fractured reservoir can be represented by a reservoir of circular symmetry having very nearly the same production history. The well radius of this circular reservoir is about 1/4 the fracture length and is essentially the same as that obtained previously for a single fluid of constant compressibility. At the same value of cumulative oil production, gas-oil ratios of fractured reservoirs producing at constant terzinal pressure are larger than those of reservoirs having no fractures. This leads to more inefficient use of the reservoir energy in fractured wells and results in lower reservoir pressures for the same cumulative oil production. The reduction in operating life due to fracturing a reservoir is not as great as that for a slightly compressible fluid. This diflerence can be accounted for by the lower reservoir pressure in the fractured reservoir and its adverse effect on the average mobility and compressibility of the oil. As anticipated, the reduction in operating life increases czs the reservoir permeability decreases. The type of results presented in this report can be used to determine the economic attractiveness of fracture treatments per se, to setect the initial spacing to be used in developing a field, and to compare the relative merits of fracturing available wells and infill drilling. INTRODUCTION The effect of vertical fractures on a reservoir producing either an incompressible or a compressible liquid has already been discussed in the 1iterature.l,2 Those results indicate that the production history of such a reservoir is essentially the same as that of a circular reservoir having an effective well radius of approximately one-fourth the fracture length. The present work reports on the effect of a vertical fracture on a reservoir producing two compressible fluids —oil and gas—by solution gas drive. Because of the empirical nature of the PVT and relative permeability data used to obtain the performance of such reservoirs, results can only be obtained numerically and with the aid of high-speed computers. Since reservoirs lose their radial symmetry when fractured vertically, pressure and saturation can no longer be given only in terms of distance from the well. Two coordinates (such as x and y) must now be used to describe the pressure and saturation within the reservoir, and, since we are dealing with compressible fluids, time is also a variable. Thus the solution of a vertically fractured reservoir requires finding two unknowns (pressure and saturation) in two space variables (say x and y) and in time (t). Since no means are readily and generally available for solving such problems at the present time, we have used the results of previous work1,2 to approximate the effect of a vertical fracture on a reservoir producing both oil and gas by depletion. The purpose of the present wmk, then, is to investigate the possibility of using available numerical techniques (limited at the moment to one space variable) to study the two-space-variable flow behavior resulting from a vertical fracture. Results obtained in the course of this investigation are also reported and discussed. Input and output data of the numerical methods used are given in practical units: BOPD, feet, psi, cp, and md. Results are discussed fist in terms of specific reservoir and crude properties and geometries. Later, dimensionless parameters are introduced in order to extend results to different values of some of the reservoir and fracture properties. IDEALIZATION AND DESCRIPTION OF THE FRACTURED SYSTEM It is assumed that a horizontal oil-producing layer of constant thickness and of uniform porosity and permeability is bounded above and below by impermeable strata. The reservoir has an impermeable, circular, cylindrical outer boundary of radius r,. The fracture system is represented by a single, plane, vertical fracture of limited radial extent, bounded by the impermeable matrix above and below&apos; the producing layer (reservoir). It is assumed that there is no pressure drop in the fracture due to fluid flow. 1 indicates the general three-dimensional geometry of the fractured reservoir. Gravity effects and the effects of differential depletion resulting from variations in hydrostatic head (pressure) will be neglected. Thus, the flow behavior in the fractured reservoir is described by the

By G. L. F. Powell

g samples of Cu-20 wt pct Ag alloy have been mdercooled to a maximum of 197°C by melting under a slag of commercial soda-lime glass in a vitreous silica crucible. No grain refinement of the primary copper was observed in samples undercooled to the maximum of 197°C. When the samples contained a small amount of oxygen, the copper dendrites were partially recrystallized at undercoolings greater than 97°C. In previous papers&apos;-3 reporting the grain structure of undercooled silver and copper, it was observed that grain refinement was dependent on both undercooling and oxygen content. Grain refinement occurred in undercooled silver when the degree of undercooling exceeded the range 153" to 175"C, while in Ag-0 alloys (0.12 wt pct) fine equiaxed grains were exhibited when undercooling was greater than 50°C. Similarly, copper samples undercooled as much as 208°C displayed fan-shaped growth from a single nucleation site, while the grain structure of Cu-O alloys (0.08 wt pct) was fine and equiaxed at undercoolings larger than 150°C. Thus the presence of oxygen greatly reduced the undercooling at which grain refinement occurred. It was also observed that the change in grain size resulted from recrystallization and was not due to an enhanced nucleation rate in the liquid-solid transformation. It is possible that the influence of oxygen on recrystallization is due primarily to its presence as a solute element. walker4,&apos; reported that, although a grain size change did not occur in pure nickel until the undercooling exceeded 150°C, small grains were observed in samples of Ni-Cu alloy solidified at small and large degrees of undercooling. Jackson et al.6 suggested that the fine grained structure of the Ni-Cu alloy resulted from the melting off of dendrite arms during recalescence. This remelting process may occur in alloys as a result of segregation during freezing which causes a variation in liquidus temperature from point to point within a dendrite. It was therefore decided to undercool copper with a metallic alloying element to ascertain whether the presence of a metallic solute would have a similar effect to oxygen in inducing grain refinement. A Cu-Ag alloy was chosen, since both metals had been shown to behave similarly on undercooling. The alloy Cu-20 wt pct Ag was selected since the eutectic constituent outlines the initial growth form of the primary copper, so that the as-frozen grain structure is not obscured if subsequent recrystallization occurs. This paper describes the results of undercooling experiments carried out with Cu-20 pct Ag samples undercooled to a maximum of 197°C and the effect of oxygen content on the grain structure of the undercooled samples. EXPERIMENTAL Melting was carried out in a small cylindrical resistance furnace using "fine" silver granulate and oxygen-free high conductivity copper. The procedure adopted was to melt the required quantity of silver in air in a clean vitreous silica crucible for approximately 15 min, freeze, and add granulated commercial soda-lime glass to form a complete surface slag cover, after which the sample was melted and frozen several times to reduce the oxygen content. The glass slag cover was approximately 3 in. thick. Pieces of copper (=50 g) were added to the crucible until the required quantity to make 350-g samples of alloy had been charged. Each piece was added quickly to the crucible which was held at a temperature slightly above the melting point of silver. The piece was quickly pushed beneath the glass to minimize oxidation and any oxide coating usually decomposed before the piece had settled down into the silver. After the full quantity of copper had been added, the melt was stirred with a silica rod to hasten homogenization and a Pt/Pt 13 pct Rh thermocouple enclosed in a vitreous silica sheath inserted for temperature measurement. Heating and cooling curves were recorded on a potentiometric chart recorder fitted with a zero suppression unit. The milli-voltage range of the recorder was adjusted so that temperatures could be read to 1°C. Heating and cooling curves were taken every hour until three consecutive readings gave the same solidus-liquidus range, consistent with the solidus-liquidus range for this alloy composition by reference to Hansen and Anderko.7 Metallographic examination of samples frozen at this stage, failed to show any variation in composition from bottom to top of the ingot. Consequently, it was considered that the melt was homogeneous at this stage and undercooling experiments were then car-

Jan 1, 1970

By K. H. Hiller

A rotational viscometer has been designed which perrnits the measurement of the rheological properties of drilling muds and other non-Newtonian fluids under conditions equivalent to those in a deep borehole (350F, 10,000 psi). The important mechanical features of this instrument are described, and its design criteria are discussed. The flow equations for the novel configuration of the viscometer are derived and the calibration procedures are described. The data and their interpretation, resulting from measurement of the flow properties and static gel strengths of homoionic montmorillonite suspensiom at high temperatures and pressures, are presented. Data are also presented for the flow behavier of typical drilling fluids at high temperatures and pressures. The pressure losses in the drill pipe and the annulus depend critically upon the flow parameters of the drilling fluid. This work demonstrates the need to measure these parameters under bottom-hole conditions in order to obtain a reliable estimate of the pressure losses in the mud system. INTRODUCTION The rheological properties of drilling fluids are affected by temperature and pressure, but the extent of these effects on the dynamic flow properties is not well known. Measurements of changes of the flow properties of clay-water drilling muds with temperature have been reported by Srini-Vasan and Gatlin.1 The temperatures reported did not exceed 200F, a limitation imposed by the apparatus used by these authors. The rheological properties of clay suspensions were measured at temperatures up to 100C by Gurdzhinian.&apos; Neither the nature of the exchange ions in the clay suspensions nor the degree of purity were defined in his work, nor were the measurements extended to currently used drilling fluids. The lack of systematic measurements of dynamic flow properties at high temperatures and pressures seems the more surprising since during the last decade the importance of the control of the hydraulic properties of drilling fluids has come to be widely recognized. Very good mathematical treatments of the friction losses in drill pipe and annulus have been developed.3 4 These treatments are based on the assumption that drilling fluids behave as Bingham plastic fluids. Quite often this assumption is justified, while in other cases a power law equation pro- duces better fit than the Bingham model does. For convenience in applying viscometer data to pressure-drop calculations, the Bingham plastic flow equation is preferable and, therefore, has been applied to the data reported in this paper, although other equations may fit these data more accurately. In a Bingham plastic fluid the relationship between the shearing stress 7 and the rate of shear D is given by the following equation: where is the plastic viscosity and 4 the yield point. If 4 = 0, the equation for simple Newtonian flow, 7 = pD, is obtained. Two empirical constants are required for the description of laminar flow of a Bingham plastic fluid, and calculations of the flow behavior at high temperatures and pressures cannot be better than is permitted by the accuracy with which these constants are known. For this reason a high-pressure, high-temperature rhe-ometer has been designed to measure the plastic viscosity the yield point +, and the static gel strength S, at pressures up to 10,000 psi and temperatures up to 350F. The important features of its design will be described. The results of measurements on homoionic clay slurries will be discussed insofar as they are relevant to an understanding of the general flow behavior of clay-water drilling fluids. The results of measurements on some typical drilling fluids will be presented also, and their practical implications will be briefly discussed. DESCRIPTION OF EQUIPMENT MECHANICAL FEATURES A viscometer designed to measure the plastic viscosity, yield point and gel strength of non-Newtonian fluids must permit the measurement of the shearing stress t at any given rate of shear D. This is possible only if t and D are approximately uniform throughout the entire sheared sample. A Couette apparatus is the most convenient method of realizing this condition, as has been pointed out by Grodde." The "high-pressure, high-temperature rheometer" described in this paper is basically a rotational Couette viscometer that is immersed in a cell in which pressure and temperature can be controlled over the range of interest. Fig. 1 shows schematically the important features of the pressure cell and associated equipment. The heart of the instrument is the rotating cup. It is shown more clearly in Fie. 2. which revresents the lower one-third of the pressure cell (below the input drive shaft shown in Fig. 1), and it is shown in detail in Fig. 3. For measurements of dynamic flow properties, the rotating cup is driven by a 1/2-hp electric motor, which operates through a Vickers

By L. D. Jaffe, F. W. Cotter, E. Cordon

The hardenability of titanium-base alloys was studied by metallographic examination and hardness survey of Jominy specimens end-quenched from the B range. Analyses of the data led to the equation log J = -0.57 + 0.25 @ct Fe + pct Mn + pct Mo) + 0.19 @ct Cr) +0.16 @ct V) + 0.03 @ct Zr). Here J is the distance, in sixteenths of an inch, from the quenched end of a Jominy hardenability specimen in the position of peak hardness, for material quenched from the B range. This equation fitted the experimental data with a standard deviation of approximately 0.29. The effects of the elements Al, Sn, W, Cu, Ni, B, C, N, 0, and H, and of pain size, were not statistically significant or not practically significant. A check against hardenability measurements in the literature showed agreement within the stated standard deviation. The equation should be useful in estimating hardenability of new or modified titanium alloys. HARDENABILITY in a titanium-base alloy is the ability of the alloy to retain the B structure on quenching. An alloy with high hardenability will retain the /3 structure even when cooled relatively slowly from a temperature at which B or P plus a is stable. A low hardenability material will retain P only if quenched extremely rapidly from the range of p or 0-plus-a stability, or will not retain it at all, at room temperature. High hardenability is desirable in titanium alloys to be heat-treated to high-strength levels. Its value is by no means limited to large section sizes. With high hardenability, a material can be solution-treated and cooled at a variety of rates, either to give high strength directly or, more generally, to give a soft ductile condition from which high strength can be obtained by subsequent aging. With low hardenability, high strength can be obtained, if at all, only by very rapid quenching, and there will generally be little increase in hardness on subsequent aging; an alloy of this type is limited in its applicability. On the other hand, alloys of very low hardenability have some advantages in weldability; essentially, they are always in the annealed condition, after welding as well as before. For commercial alloys, hardenability data are usually available, in the form either of property data after cooling from the solution temperature at various rates, with or without subsequent aging, or of results of a standard hardenability test, such as that originally developed for steels by Jominy and Boegehold.&apos; When modifications of an available alloy are considered, or preparation of new alloy compositions, it would be Very convenient to be able to estimate the hardenability of the new material without having to make and test it. A method of estimating hardenability of titanium alloys from their composition was suggested by one of the authors some time ago, on a preliminary basis, utilizing scattered data found in the literature.&apos; It seemed worthwhile to carry out a systematic experimental study of the effect of composition upon hardenability. EXPERIMENTAL PROCEDURE Approximately fifty heats of various compositions, weighing 8 to 10 Ib apiece, were melted in a small inert-gas tungsten-arc furnace with water-cooled copper walls. The starting material was 110 Brine11 titanium sponge, with high-purity metals added for alloying. Each heat was bottom-poured under vacuum through a molybdenum burnout strip into a cold graphite mold, to form an ingot approximately 4-1/2 by 3-1/2 by 3 in.* From each ingot were cut *The material was melted and cast by Pitman-Dunn Laboratory, Frankford Arsenal, to whom the authors must express their thanks. two pieces 4-1/2 by 1-1/2 by 1-1/2 in. These were forged, at temperatures adjusted to the composition, into 1-1/4-in. rounds, from which standard 1-in.-diam hardenability specimens3 were machined. A number of small samples were also prepared from forged materials of each heat, annealed, quenched from various temperatures, and examined metallographically. The P-transus temperature was determined by observation of the degree of resolution of primary a in these pieces. samples for chemical analyses were also taken from the forgings. One hardenability specimen of each heat was solution-treated for 1 hr approximately 50°F above the measured transus temperature, and the other for 1 hr approximately 250°F above the transus. (An additional hour was allowed for the specimens to reach furnace temperature.) These are not necessarily the temperatures that would be selected for

Jan 1, 1964

By R. J. S. Brown, B. W. Ganison

A new logging method has been developed, based on measurement of the nuclear magnetism of formation fluids. The nuclear magnetism log (NML) is the only log that responds solely to formation fluids. It operates equally well in both oil-base and water-base muds and in empty holes, and can be used in all kinds of formations except strongly magnetic ones. Two separate NML measurements can be made, one of which provides a continuous formation fluid curve. This fluid curve is called the free fluid log (FFL) and is believed to indicate a minimum effective porosity in most formations. The FFL not only delineates fluid-containing zones, but provides an excellent correlation curve that can be obtained under conditions where conventional correlation logs are ineffective. Preliminary tests indicate that the second kind of NML measurement may help distinguish oil and water zones and provide information concerning permeability and wettability. (The FFL itself appears to provide some information on permeability.) The second kind of NML measurement requires stopping the logging tool for a short time opposite a zone of interest and taking more extensive NML data that can be displayed as nuclear magnetic relaxation curves. In some instances, oil and water saturations for the region immediately adjacent to the borehole can be read from these relaxation curves. INTRODUCTION In 1946, Bloch, Hansen and Packard and Purcell, Torrey and Pound3 independently announced the successful demonstration of the phenomenon of nuclear magnetic resonance. During the past 13 years, there have been many applications of nuclear magnetic resonance, including applications to the study of chemical structure and to the measurement of magnetic field strengths. Preliminary experiments on the feasibility of using nuclear magnetism measurements in well logging were made independently by California Research Corp. and Varian Assoc., the Varian work being sponsored by the Byron Jackson Tools, Inc. Since then a cooperative research program on nuclear magnetism logging has been carried out by the Byron Jackson Div. and Research Center of Borg-Warner Corp., and California Research Corp., subsidiary of Standard Oil Co. of California. The use of nuclear magnetism in well logging is of special interest because it offers a way of making direct measurements on the hydrogen in the formation fluids and not on the rock matrix. Within the past 1 1/2 years, successful measurements have been made with a research model logging tool in wells in California, Tex as, Utah, Louisiana and Wyoming. NUCLEAR MAGNETISM SIGNALS Polarization, Relaxation and Precession Many atomic nuclei possess magnetic moments and spins; that is, they are similar in some respects to bar-magnet and gyroscope combinations. Molecules and their nuclei are subject to thermal motion, which has a scrambling effect, tending to leave as many nuclear spins oriented in any one direction as in any other. However, if a magnetic field is applied, the magnetic nuclei tend to align in the direction of the field. The scrambling and aligning forces compete with each other, with the result that a few more spins are oriented parallel to the field than in other directions. This gives a net magnetization, or polarization, which is directly proportional to the strength of the applied magnetic field (aligning influence) and inversely proportional to the absolute temperature (scrambling influence). When the magnetic field in, or temperature of, a liquid sample containing protons is changed, the new equilibrium value of proton polarization is not established immediately but requires an amount of time which depends on the nature of the hydrogen-containing materials. The process of approaching the equilibrium value of polarization is called relaxation.&apos;.&apos; Polarization is a vector quantity, and the components parallel to and perpendicular to the magnetic field must be considered separately. Relaxation of the component parallel to the field is called "thermal relaxation", or "longitudinal relaxation", and the corresponding time for this component of non-equilibrium polarization to decay by a factor of e (natural log base) is denoted T. The relaxation of the perpendicular component is called "transverse relaxation", and the corresponding relaxation time is denoted T,. The potential energy of a magnet in a uniform field depends on the angle the magnet makes with the field; therefore, a change of the component of net polarization parallel to the magnetic field involves an exchange of energy between the spin system and the thermal motion of the molecules, leading to the term thermal relaxation for the relaxation of this component. Suppose we subject a sample to a strong magnetic field at right angles to the earth&apos;s field for a time greater than TI. A polarization, thus, is established at right an-

By D. L. Archer, W. W. Owens

Conventional waterflooding often is uneconomic in highly fractured reservoirs because of the gross bypassing of the reservoir oil by injected water. Imbibition and pressure pulse flooding have been used in at least one fractured reservoir in an attempt to achieve better oil recovery performance. This paper presents the results of laboratory flow tests conducted on large cores to evaluate the possible applicability of these methods (particularly pressure pulse flooding) to different types of reservoir systems. Test data were obtained on both water-wet and oil-wet systems, and on systems having two widely different levels of compressibility and flow capacity. Results indicate that pressure pulse recoveries from fractured reservoirs will likely not exceed 5 to 10 per cent pore space with maximum response achieved during the first pulse cycle. Improved recovery by this method is possible from both oil-wet and water-wet reservoirs. Comparable saturation distributions during imbibition and pressure pulse production suggest that an initial pressure pulse cycle to speed production response would not interfere with subsequent imbibition flooding in water-wet reservoirs. INTRODUCTION There is a steady increase in the number of fluid injection projects being initiated each year to improve oil and gas recovery over that obtained by primary production mechanisms. Experience gained in different geographical areas and with different recovery methods is teaching that reservoir anatomy is one of the more important factors controlling the success or failure of such projects. Fractured formations appear to be the rule rather than the exception, especially in carbonate reservoirs. Conventional methods of fluid injection, whether it is waterflooding, gas injection or miscible flooding, have limited applicability to highly fractured reservoirs because of the severe bypassing of reservoir fluids. The result is early breakthrough of the injected fluid and rapidly increasing ratios of injected to in-place fluid with an undesirable effect on return on investment. Thus, innovations to conventional methods must be developed if recovery from fractured reservoirs is to be optimized. One new method proposed for application to highly fractured reservoirs is pressure pulse waterflooding. Although pressure pulsing with gas has been suggested&apos; and rested in at least one reservoir; the Sohio Oil Co. is generally credited with the development and testing of pressure pulsing in conjunction with waterflooding. Publications" of Sohio&apos;s waterflood operations in the Spra-berry Trend indicate that the idea for pressure pulse flooding evolved from a critical analysis of the disappointing early performance of their flood initiated in a portion of the trend in April, 1961. This flood was planned to take advtantage of imbibiltion and high pressure gradients across the reservoir matrix blocks (unfractured Mocks of the reservoir rock which are visualized to be generally surrounded &apos;by the fracture system) evaluated in pilot tests by the Atlantic Richfield Co.5 and Humble Oil & Refining Co.&apos; However, the early recovery and pressure performance of this flood indicalted that high pressure gradients induced between the fracture system and the centers of the matrix blocks were forcing water into the periphery of the blocks and temporarily interfering with the counter-current flow of oil due to imbibition. Fill-up in the blocks was occurring with re-solution of the free gas phase as pressures climbed above the original reservoir bubble point. It appeared that cessation of water injection to permit the capillary forces to become dominant and that expansion of the rock and its contained fluids during pressure reduction might aid in expulsion of oil from the rock matrix into the fractures. Subsequent production performance. aflter cessation of injection, proved this hypotheslis correct. Thus, pressure pulse waterflooding was born. Pressure pulse flooding appears to have several advan&apos;tages over imbibition type flooding in highly fractured reservoirs. First, all wells may be used for water injection which should hasten fill-up and achieve a more rapid increase in reservoir pressure. Second, because of increased injection pressures and rates, flooding gradients will force water into the reservoir matrix more rapidly than would be achieved by imbibition alone. Third, during the pressure depletion cycle of the flood, the compressibility of the system, which has been increased by resolution of the free gas phase, provides energy for the displacement of oil at a rate greater than would correspond to countercurrent flow during imbibition. Fourth, during depletion all wells may be put on production, thus contributing to higher oil withdrawal rates on a reservoir-wide basis. One possible disadvantage of pressure pulse flooding as compared to imbibition floodling, however, is that the outer periphery of each matrix block is flooded to a residual or near residual oil saturation during the Water lnjection stage. This zone of reduced permeability to oil m&apos;ay offer greater restriction to the production of

Jan 1, 1967

By F. M. Morris

A large reserve of thick coal in southwest Virginia was developed by Clinch-field Coal Co. in 1957-1958 to produce a nominal rate of 1500 tph raw coal. Operation features coal cleaning in transit. Refuse removed averages 35 pct. Evolution of plant from initial conception to completion is discussed, selection of means applied is explained, and performance to date us design expectation is described. The long-range plan calls for ultimate handling capacity of 40,000 tpd raw coal with anticipated clean coal capacity of 26,000 tpd on a three-shift basis. From a materials handling viewpoint, the Moss No. 3 operation is principally of interest as an ensemble. Generally speaking, it uses time-tested equipment and ideas but some of these are employed on a scale that may be new in the industry. At present about 20,000 tpd of raw coal are being handled. This is expected to increase to 40,000 tpd as soon as business conditions justify it. The purpose of this paper is to discuss the evolution of the plant as to materials handling practices, to describe briefly the equipment and methods used, and to comment on performance in certain areas. The subject divides itself naturally into four phases: 1) operations at the mines, 2) transportation from mines to plant, 3) raw coal handling into the plant, and 4) transportation of refuse away from the plant. OPERATIONS AT THE MINES The coal reserves for Moss 3 are in southwest Virginia where Dickenson, Russell, and Buchanan Counties come together. This area contains about 15 square miles and over 100,000,000 tons of coal. Here the No. 4 (Tiller) and No. 5 (Jawbone) seams of the Norton Formation lie so closely together that for practical purposes, they constitute one seam of coal. This seam, which is called the Thick Tiller, varies from 10 to 18 ft in thickness and underlies Sandy Ridge, a mountain cresting between 2400 and 3300 ft above sea-level. At 18-ft seam height (which is considered to be the maximum practical mining height) the parting between seams will be about 3 1/2 ft thick and each bench of coal will be about 7 ft thick. Depending on the amount of impurities in the seams Drover. total reject in this height coal may approximate 50 pet by wt. It will average about 35 pet for the property as a whole. The first move in developing this resource was made in 1953 when contour maps of several square miles around Duty, Va., including all the known outcrop, were made by photogrammetry. At this time, it was felt the prospective operation would be served by the Clinchfield Railroad and a photogrammetric route survey was made by this railroad from Haysi to Duty. Study of the resulting maps indicated only one site—adversely owned—which might accommodate the size washing plant to be erected. Water resources of a dependable nature seemed nonexistent. In 1954 bulk washability tests were made on the Tiller Bench at the Moss No. 1 preparation plant. The tests indicated this portion of the seam, mined separately, would wash to 4 pet ash with good recovery. Also in 1954, development of Moss No. 2, south of Sandy Ridge, was begun. This mine is in the Tiller Seam where it is about 100 ft below the Jawbone Seam. The reasons for developing a mine in the normal Tiller Seam before tackling the Thick Tiller seemed compelling: Railroad service could be established quickly, communications were better (though not good!), more was known of the seam (it had been mined in the years 1911 to 19241, and there was no essential property to be acquired. After some legal skirmishing, the Norfolk & Western Railroad was granted the right to serve the new mine. Three decades earlier the old mine had been served by the Clinchfield Railroad. The event which triggered active development of Moss 3 was the Appalachian Power Co.&apos;s decision in 1956 to build a 450,000-kva power plant on Clinch River at Carbo. This solved the problem of marketing the steam coal which inevitably must be a product of a mine in the Thick Tiller. Management promptly decided to build the preparation plant at Carbo where an excellent site was owned; where railroad service existed; where telephone service could be obtained; and where roads, bridges, and water supply were tolerable.

Jan 1, 1961

By William Campbell

(Cleveland Meeting, October, 1912.) [SECRETARY&apos;S NOTE.-To avoid repetitions of foot-notes, references to authorities are made in the paper by means of figures, referring to a numbered list in the appendix.-J. S.] I. INTRODUCTION. IN the olden days the making of alloys was au art, and the secrets of the craft were jealously guarded. To-day it has become a science, though the old ideas in regard to the secrets and formula are dying hard. Modern progress may be attributed to scientific research and testing of materials, and the substitution of chemical analytical control for " cook-book " methods. We know to-day a great deal about the constitution of alloys, the reasons of the change in structure and physical properties by heat and mechanical treatment; and this new knowledge is due for the most part to the physical chemist and metallographist, who have shown us that alloys are simply solutions, and as such obey definite laws. The application of the theories of solutions and of the phase rule tells us what ought to happen when our alloys are in a state of equilibrium. The working-out of the temperature-composition diagram (thermal diagram) for numerous alloys has thrown a light on the structure and constitution which has dispelled most of the darkness in which we labored before the advent of metallography. The work began with the determination of the freezing-point curves, and here the research of Le Chatelier,1 Gautier,2 Roberts-Austen,3 and the other pioneers broke the ground. Next the physical chemists, Tammann,4 Rooseboom,5 Bancroft,6 and their colleagues, showed us the complete thermal diagram and its meaning. Then the researches of Heycock and Neville 7 on the Cu-Sn series and of Shepherd 8 on the * Associate Professor of Metallurgy, Columbia University in the City of New York.

Dec 1, 1912

By JOHN LANE DYNAN

HE Tonopah Extension property consisted originally of three claims, with an area of 38 acres. In 1902 a shaft, now known as No. 1, was started near the eastern end of the property, close to the Tonopah Mining Co.&apos;s boundary line, in the. andesite cap rock&apos; which covers the ore-bearing formations in the western end of the Tonopah district. A short distance below the 60-ft. level, the orebodies pinched out, although the veins continued. This shaft has not been used since 1916. Before 1910, the production was small, coming mostly from small shoots of high-grade shipping ore. In that : year, the, company started its 30-stamp mill and cyanide plant; the mill was later enlarged to 50 stamps, with a corresponding increase in the cyanide-plant capacity, which brought the capacity of the mill up to 350 .tons per day. The total production of the mine to Oct. 1, 1920, is 871,177 tons of ore, from which was recovered 15,267,216 oz. of silver and 156,241 oz. of gold.&apos; This makes an average recovery per ton of 17.5 oz. silver and 0.179 oz. gold. The average price received for silver since&apos; the beginning of operations is 65.87 c. per oz., and the average value recovered from the ore-&apos;is $15.25. The area of the property has been gradually increased by purchases and consolidations of adjoining ground until it is now 647 acres. A new shaft, known as No. 2, was started in 1912, 1600 ft. west .of No. 1, and in the following year a crosscut on the 750-ft. level of this shaft resulted in the discovery of the. Murray Vein system, from which the greatest prosperity of the mine has come. This vein, with its related veins,

Jan 1, 1921

"With a total value to date of well over $200,000,000.00 for its ore production, the Tintic mining district, which is about 100 miles southwest of Salt Lake City, ranks as one of the three main ore producing areas of Utah. In it are located the biggest silver mines of the country, silver having been the chief metal produced in the camp since its start. Tintic's silver production to date has a total value of over $ 100,000,000, approximately half of the value of the camp's ore production, the balance being roughly divided among lead, gold and copper.Discovery of the camp was made in the late sixties. Lack of transportation and ore reduction facilities delayed extensive development of the area for nearly a decade.In recent years Tintic's ore production has ranged from 350,000 to 400,000 tons annually. In 1 924 the camp produced one-eighth of the silver produced in the nation with an output of 7,729,700 ounces. Its lead production was 77,765,000 pounds and its gold production 26,285 ounces.The known mineralized area of the district is found in a broad syncline striking north and south. The west limb plunges sharply and extends for a distance on its dip of approximately one and a half miles to the trough. The east limb raises gently through a distance of about two miles to the east limit of known mineralization. This general structure is broken by local faulting throughout the district, the local structural conditions playing an important part in the ore deposition. The north end of the fold is obscured by a rhyolite flow and the south end stops against a monzonite stock."

Jan 1, 1925

By ERNEST A. HERSAY

ACCURATE ore-sizing with screens is drawing attention to certain details that now, more than ever before, require attention. There are many tests that must be preceded by careful sizing. The assayer often could profit by a more careful selection of screens. In milling, more attention is given the slimes produced. Cement-manufacturers are pulverizing and screening finer than they formerly did, and others are reducing materials to fine sizes at high cost, with screens used to govern the fine¬ness of the pulverized product. Fine screens are expensive, easily injured by mis-use, are carried in stock sparingly by most dealers, and are handled often by those who know little about them except their designated number. More attention, on the whole, needs be given the actual size of the mesh-openings, and less emphasis placed upon any custom or conventionality in numbering. An effort to classify wire screens, in this respect, leads at once into computations, where one is confronted with details of sizes and standards, of different wires, different gauges, and different customs. There is always uncertainty about the exact working-size of a screen until one gives the matter special attention, and devotes more time to it than its simplicity seems to demand. To know only the number is not sufficient for all uses. Often, in sets, superfluous sizes are used; and sizes are omitted that are of critical importance. In wire screens, the use of different standard sizes of wire makes important differences in dimensions that must be taken into account. The dealer usually grades screens by the number of openings per linear dimensions, regardless of the size of the openings or of the wire. Certain 100-mesh screens in use are found, by measurement, to he actually coarser than others of 90-mesh, a result which is due, of course, to the use of larger

May 1, 1906