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By W. A. Ver Wiebe

Under the impetus of new demands caused by the war, the oil and gas industries of Kansas established new records during the year 1942. In all, 1513 test wells were drilled, which is somewhat of a drop from the figure of 2113 for 1941. The 1513 tests yielded 800 new oil wells, 85 new gas wells, and 628 dry holes. Thus there was an increase in two categories, the gas wells and the dry holes. Considering that last year only 592 dry holes were completed out of a much larger total, the figure of 628 dry holes causes some concern among local operators. The increase in unsuccessful tests illustrates once more the fact that each year it is becoming harder to find the remaining oil pools. When the figures are broken down, it appears that western Kansas accounted for 1177 tests, of which 689 were oil wells, 33 gas wells, and 455 dry holes. The total potential daily initial production uncovered by the successful wells amounted to 753,178 bbl. of oil and 619,734,000 cu. it. of gas. The figures for new initial production indicate a substantial drop from last year's figure of 1,691,000 bbl., and the figures on gas are slightly higher. In 1941 the new gas as based on a daily potential was 508,000,-000 cu. ft. In eastern Kansas, 336 wells were drilled. Among these in were oil wells, accounting for a daily initial potential production of 16,199 bbl. The new gas wells numbered 52 and added 253,725,000 cu. ft. per day to the gas potential production of the state. The remaining tests, 173 in number, were dry. It is interesting and perhaps significant that about half (630) of the wells drilled in western Kansas were drilled by the independent operators. Among the large companies, the Cities Service Oil Co. drilled 163 wells; the Stanolind Oil and Gas Co., 52; the Skelly Oil Co., 39; the Continental Oil Co., 48; and the Shell Petroleum Co., 21 wells. In eastern Kansas the independent operators drilled 297 out of the total of 336 wells. Among the major oil companies the Cities Service Oil Co. drilled 19; the Phillips Petroleum Co. 7; and the Sinclair-Prairie Oil Co., 6 wells. The figures based on relative percentages of dry holes to successful oil or gas wells are revealing. In western Kansas almost one half of all wells drilled by the independent operators were dry holes. The major oil companies drilled approximately 547 wells in western Kansas, of which 379 were successful in finding either oil or gas. It thus appears that the major companies fared better than the independents. In eastern Kansas the major companies drilled 39 wells, of which 29 were successful in finding commercial quantities of oil or of gas. No less than 329 wildcat test holes were put down in western Kansas and 105 in eastern Kansas, or 434 in all, during 1942. Considerably more than half of these were drilled by independent operators; 223 in western and 99 in eastern Kansas. An exploratory hole 56 mile or more from production is regarded as a wildcat well in Kansas. On a percentage basis, about 80 per cent of wildcat wells were failures. In western Kansas only 20 per cent found either oil or gas. The failures were about equally distributed among the major

Jan 1, 1943

By P. Pollard

A method has been developed for evaluating acid treatments in fractured limestone fields by breaking down pressure drawdown into three component parts: (I) pressure differcntial across "skin" near the borehole face, (2) pressure differential due to flow resistance in the coarse communicating fissures and (3) pressure differential between the fine voids and the coarse fissures. It is apparent that in most successful acid treatments the first term, skin resistance, has been reduced or eliminated. Further, it is often possible to estimate the volume of coarse fissures associated with the second term, coarse fissure flow resistance. In cases where this volume is comparable with practical acid volumes it seems likely that this resistance also may be attacked with a suitably retarded acid. INTROD UCTION Acid treatment has been successfully applied as a general practice in the limestone wells in the Mara/ Maracaibo districts of Venezuela for some 10 years. At the same time the need has been felt for a more precise method of: (1) evaluating the effect of an acid job and (2) selecting wells which should benefit from an acid treatment. The following method, based on an analysis of build-up curves for wells producing from fractured limestone, provides a means of forecasting the effect acid will have on a well and in many cases the probable order of production rate increase which may be expected. In certain cases it is also possible to calculate the fissure volume through which the acid has to be displaced for best results. Various approximations are introduced in the method, but within the limitations of these the analysis gives an indication of how a well, whether previously acidized or not, may be expected to respond to acid treatment. Suitable build-up curves cannot be obtained on "tight" wells which do not give sustained production and the method is not applicable to such wells. Figs. 1 through 7 illustrate various types of build-up curves obtained from limestone wells in Western Venezuela. Curves are included showing (1) both skin and coarse fissure resistance, (2) skin resistance only, (3 and 4) reduction of skin resistance by acidization, (5) fissure resistance only, (6) reduction of coarse fissure resistance by acidization, and (7) acidization failure. This theory has been successfully applied for over three years during which 22 acid treatments have been carried out specifically to reduce skin resistance and three treatments to reduce coarse fissure resistance. The method has been found to be a useful aid in the selection of wells for acidization.

By Y. H. Liu, G. W. Powell

Thin foils made from the gold-rich region of- short (0.15 mm)Au-Ag diffusion couples annealed at 880°C for 1 hr were examined in ax electron microscope and the structures were compared with that of pure gold subjected to identical heat treatments. The couples underwent Plastic deformation (bending) during the diffusional anneal. The foils prepared from the diffusion zone have a higher dislocation density and incidence of subboundaries than pure gold. The plastic bending of the couple can be interpreted in terms of the climb of edge dislocations, which are pavallel to the bend axis, along the direction of diffusion. THE interaction of lattice defects during interdiffu-sion between two metals has been considered by several investigators. In particular, da Silva and Mehl,1 Barnes,' and Bardeen and Herring3 have proposed models based on interactions between point and line defects to account for the Kirkendall effect (marker movement). Each of these models is based on dislocation climb, which can either add or remove lattice planes, induced by an under- or supersaturation of vacancies. A theoretical treatment of the nucleation and growth of voids by the condensation of vacancies has been presented by Seitz.4 Stresses can arise in a binary diffusion couple as a result of the vacancy flux and the gradient in the lattice parameter. rinkmman' has investigated the effects of diffusion-induced stresses on void formation; the results of his analysis suggest that voids can form and grow under the influence of these stresses in the absence of an excess vacancy concentration. The relationships between vacancy supersaturation and diffusion-induced stresses and void formation have been elucidated also by Balluffi and seigle6 who concluded that the stress generated by a vacancy supersaturation aids the growth of voids. Experimental evidence which indirectly shows that stresses are produced by chemical diffusion has been obtained by several researchers.2,7-9 This evidence consists in part of the observation by light microscopy of the formation of subgrains, a process characteristic of the high-temperature deformation of some metals during creep.'0 More striking, however, is the plastic bending of short (0.2 mm) Cu-Ni couples observed by Barnes2 and of boron-doped silicon crystals reported by Queisser.9 Diffusion-induced dislocations in iron and silicon have been investigated by Ainslie et a1.11and Schwutte and Queisser,12 respectively, the former using transmission electron microscopy and the latter an X-ray transmission technique. Matthews and Crawford13 observed the formation of boundaries by the climb of interfacial misfit dislocations in thin, vapor-deposited Au-Pd couples diffused in situ in an electron microscope. In order to obtain additional information on the phenomena associated with defect interaction and diffusion-induced stresses in binary couples, an electron transmission study of foils prepared from the diffusion zone of short Au-Ag couples was undertaken. The initial objective was to investigate the processes occurring at various points of the diffusion zone. Subsequent research demonstrated that foils could be prepared only from the gold-rich region of the diffusion zone using the technique described herein. EXPERIMENTAL PROCEDURE Preparation and Annealing of the Diffusion Couples. The couples were made from annealed, high-purity (99.999 pct). polycrvstalline gold and silver sheets (0.075 mm thick). Shall (0.075 by 5 by 17 mm) elec-tropolished coupons of gold and silver were pressure-bonded by heating the two metals in a graphite device to 770°C and holding at this temperature for approximately 30 min. The quality of the bond was ascertained by metallographic examination at 150 times. Each couple subsequently was annealed at 880°C for 1hr; under these conditions, the extreme portions of the

Jan 1, 1968

By G. J. Heuer, J. N. Dew, G. C. Clark

The effect on well behavior of partial permeability barriers, changes in producing rates and well spacings have been calculated through use of a radial, unsteady-state, two-phase-flow mathematical model. This model allows for variations in permeabilities and porosities with distance from the wellbore. The numerical methods necessary to solve the problem require use of a highspeed digital computer, in this case an IBM 704. In each instance, pressure and saturation gradients, gas-oil ratios and recoveries around a well producing by solution-gas drive have been calculated as a function of time and distance from the wellbore. Comparisons are made to show the effect of changes in producing rate and of varying permeability near the wellbore and out in the formation on the production and pressure history of the well. The effect of different well spacings on producing rate and ultimate recovery is considered. Although the mathematical description of the reservoir is simplified in comparison to an actual reservoir, the results do give some insight into the difficult problem of spacing and proration in a heterogeneous solution-gas-drive reservoir. Results show that for the cases considered spacing has little effect on ultimate recovery and that permeability barriers removed from the well decrease producing rate for a period of time but have only a small effect on ultimate production. INTRODUCTION The effect of spacing and producing rate on the production characteristics and ultimate recovery of a well producing by the solution-gas-drive mechanism have been topics of interest to the oil industry for many years and the subject of many hearings before state regulatory bodies. The problem is very complicated because of the difficulty of simulating in the laboratory a reservoir producing by the solution-gas-drive mechanism under anything like normal field conditions. This paper gives the initial results of a study aimed at determining the effect of these factors on production from reservoirs simulated by a mathematical model. Two-phase, unsteady-state equations are used to calculate pressures, saturations, and rates of oil and gas flow as a function of time and distance from the wellbore. The model is radial, and reservoir properties may be varied with distance from the wellbore. A decrease in permeability at a given distance results in a low-permeability ring concentric with the wellbore through which all the fluids from more distant portions of the reservoir must flow. The current mathematical model allows for variation of permeability, porosity and saturations as a function of distance from the well. Any desired drainage radius for the well may be selected. Drainage radii of 745 and 1,053 ft, which correspond to 40- and 80-acre spacing, were chosen for the calculations which follow. A large amount of the input data has been held constant. No investigation was made into the effect of changes in fluid properties and relative permeability characteristics on oil and gas production behavior. Fluid properties and relative permeabilities are essentially those of the White Mesa portion of the Greater Aneth area in southeastern Utah. A recently concluded hearing before the Utah Oil and Gas Conservation Commission to determine spacing for the field aroused interest in the possible effect of permeability constrictions located some distance from the well on production and recovery. This interest stimulated the present study. In this paper, no attempt has been made to simulate any field production characteristics exactly. Only the solution-gas-drive mechanism has been investigated, and production by liquid expansion has not been considered. This investigation is exploratory in nature but does give some insight into the problems of spacing and proration in a solution-gas-drive field having permeability variations. THE MATHEMATICAL MODEL The mathematical model is similar to that proposed by West, Garvin and Sheldon.' Approximately the same techniques have been used in arriving at a solution. The equations are nonlinear, partial differential equations which have been known for some time. The particular equations used for this study neglect the effects of capillary pressure and gravitational forces. The advent of modern digital computing equipment has made their solution practical. Basically, the method solves for pressure, saturations, and oil and gas flow rates as a function of distance and time. In our model, distance to the

By J. P. Morris

PREVIOUS investigations1,2 have shown that alloying elements in liquid iron influence the thermodynamic activity of sulphur and thereby affect the partition of sulphur between metal and slag in the desulphurization process. For example, the greater efficiency of desulphurization in the blast furnace as compared to the open hearth can be attributed in part to a higher level of sulphur activity in blast-furnace metal due to the higher concentration of carbon and silicon. In the present investigation, a short study was made of the influence of manganese on the activity of sulphur in liquid iron and iron-carbon alloys. In contrast to carbon and silicon, manganese was found to decrease the activity coefficient of sulphur; and in iron-carbon alloys it counteracts to some extent the influence of carbon. However, at manganese concentrations normally present in the blast furnace or open hearth, the effect of manganese is small. Since manganese sulphide has a limited solubility in iron, manganese can act, under certain conditions as a desulphurizing agent. Considerable data on the manganese-sulphur product in carbon-saturated melts were obtained in the investigation and have been included in this report. The experimental procedure was the same as that used in the earlier investigations on the effect of silicon' and carbon' on sulphur activity. Briefly, the method was as follows: The molten alloy, contained in a graphite or sintered alumina crucible, was brought to equilibrium at a constant temperature with a mixture of hydrogen and hydrogen sulphide of constant composition by bubbling the gas through the metal. Samples of' the melt were taken for analysis at regular intervals by suction through a 2 to 3 mm bore silica tube dipped into the metal. The experiments were run in a graphite spiral resistance furnace with melts weighing 50 to 60 g. The gas bubbling tubes were made of sintered alumina and were 5/16 in. OD, 1/16 in. ID, and 24 in. long. Equilibrium was assumed to have been attained when the sulphur content of the liquid metal reached a constant value. During an experiment there was a rapid loss of manganese from the melt by volatilization. To offset this loss, small additions of manganese were made periodically. The rate of manganese addition needed to maintain a constant manganese concentration was determined in preliminary tests. In all of the experiments, deposits of manganese sulphide formed above the melts in a cooler region of the furnace. Apparently, these deposits resulted from a reaction between manganese vapor and hydrogen sulphide in the gas. To prove that manganese sulphide did not volatilize from the melts to a measurable extent, an experiment was run in which helium was bubbled through liquid iron containing both manganese and sulphur. Although manganese volatilized rapidly in this test, there was no appreciable loss of sulphur. Volatilization of manganese sulphide from a melt would have led to an apparent equilibrium condition in which the sulphur content of the metal was lower than the true equilibrium value. The experimental results are shown in the first seven columns of Table I. The data in the last two columns were obtained from the previous work on the effect of carbon' and show what the results would have been in the absence of manganese but with temperature, gas composition, and carbon content of the metal remaining the same. Comparison of the last four columns show that, in the presence of manganese, the sulphur content of the metal increased at equilibrium and the activity coefficient of sulphur decreased. However, the results show that, for manganese concentrations below 3 pct, the effect of manganese is small. The values for activity coefficient of sulphur given in Table I were calculated from the following relations: S (in liquid metal) + H2 (gas) = H2S (gas) [l] K ph2s/?s X %S X phg = 0.00251 [2] where K is the equilibrium constant for the reaction, PH2S and ph2 are the partial pressures of hydrogen sulphide and hydrogen, respectively, and ?s is the activity coefficient of sulphur. The standard state for sulphur was taken to be a 1 pct solution of sulphur in pure iron. The numerical value for K at 1600°C was determined in the earlier work. For the purpose of showing graphically the results of the tests run at 1600°C, the activity coefficients of sulphur were recalculated so as to correspond to a manganese concentration in the metal of 2 pct in each case. In the calculation it was assumed that the increase in sulphur content of the metal at equilibrium caused by the presence of manganese

Jan 1, 1953

By H. A. Koch, R. L. Slobod

This paper discusses a new oil recovery process called the "miscible slug process." This process involves the injection of propane or LPG into the reservoir prior to gas injection. The operating conditions are maintained so that the slug is miscible with both the reservoir oil and the injected gas phase. Thus, a miscible phase displacement is achieved, and high recoveries are obtained from the area of the reservoir contacted. The most striking discovery of the laboratory study which included displacements from cores up to 123 ft in length was that relatively small slugs of LPG are effective over reservoir distances in the miscible displacement of oil. This makes possible the commercial application of the process. The important factors controlling the size of the slug are: (I) reservoir length, (2) reservoir fluid composition, and (3) reservoir pressure at the displacement front. Of lesser importance are the effects of injection rate and porous medium type. Questions which have not been completely answered deal with the effects of gravity and reservoir inhomogeneities on the process. INTRODUCTION One of the major problems facing the oil industry today is recovery of the large fraction of the discovered oil which will remain unrecovered unless some new processes are found. Water flooding has been one successful method used to increase recovery over natural depletion. But even successful water floods may leave 25 to 40 per cent of the pore space filled with residual oil. Recently a process which involves the use of thermal energy has been reported1,'*' which may prove useful in increasing recovery from shallow reservoirs containing highly viscous crudes. This paper deals with a new oil recovery process involving use of miscible phases to displace the oil from the reservoir. Miscible phase displacement oil has been an intriguing idea because the elimination of capillary effects in the reservoir leads to 100 per cent recovery in the areas contacted by the miscible displacing phase. The big deterrent in the past to the practice of miscible phase displacement has been the high cost involved in using large volumes of solvent in the process. The use of high pressure gas to achieve a miscible phase displacement of reservoir oil has been reported4,5 as one economically feasible method. However, this process calls for the maintenance of pressures above 3,000 psi at the dis-placement front. The process described in this paper is not restricted to high reservoir pressures; the only qualification being that the slug of material which is injected into the reservoir must be miscible with both the displaced oil 2nd the displacing phase. Two such cases are the use of an alcohol slug followed by water to achieve a mis-cable water flood, and the use of a low boiling hydrocarbon slug such as propane followed by gas to achieve a miscible gas drive. This paper will deal specifically with the propane dug process. This process will obtain a miscible phase displacement at pressures as low as about 1,200 psi at a reservoir temperature 01 150°F. The process is very simple. The propane displaces oil completely at one front because it is miscible with the oil, and gas displaces the propane completely at a second or trailing front because it is miscible with the propane. A small band of propane should thus remain wedged between the gas and oil phases. This idea has been called the "miscible slug process."6 Unfortunately, the propane slug will become diluted as it flows through the reservoir. This results from a mixing action since the fluids flow through a complex reservoir porous medium rather than simple capillaries. Fig. 1 diagrams a miscible slug displacement. The effects of some of

Jan 1, 1958

By Joseph B. Story, John T. Clarke

A modification, of the Kelvin bridge using an inductor was used to measure the conductivities of molten sodium chloride, calcium chloride, and mixtures thereof. A capillary-type four-lead fused quartz dipping cell was constructed. The effect of a small amount of potassium chloride on the conductivity of the melt was determined. IN the electrowinning of sodium and chlorine from sodium chloride in Downs cells, calcium chloride is added to the sodium chloride in an approximately equimolar amount to permit cell operation at a lower temperature. This lower temperature improves current efficiency and ease of operation, but decreases voltage efficiency by decreasing the electrical conductivity of the melt. A knowledge of the electrical conductivity of the Downs cell melt is necessary to the understanding of Downs cell operation, for the IR voltage drop across the melt is responsible for a significant part of the electrical power consumed by the cell. The work of previous investigators on fused sodium chloride-calcium chloride mixtures was reviewed from the standpoint of consistency with the results of others on the conductivities of the pure constituents. The electrical conductivity of pure fused sodium chloride has been established with accuracy by Van Artsdalen and Yaffe,1 by Edwards, Taylor, Russell, and Maranville,2 and by Lee and Pearson.3 It has also been studied by a number of other investigators.4-13 The best values for calcium chloride are believed to be those of Lee and Pearson,3 since the sodium chloride and potassium chloride conductivity values given by them check the best literature values. A number of other investigators have also reported values for calcium chloride.'-"."' Electrical conductivity data for fused sodium chloride-calcium chloride mixtures have been reported by Sandonnini,12 Vereshchetina and Luz-hnaya,18 Ryschkewitsch,11 Barzakovskii,5 and Alaby-shev and Kulakovskaya.15 Sandonnini reports no data at temperatures lower than 850°C. The conductivity values reported by Vereshchetina and Luz-hnaya, by Ryschkewitsch, and by Barzakovskii for pure sodium chloride and for pure calcium chlor- ide vary somewhat from the literature values believed to be best and the sodium chloride-calcium mixture data of these authors and of Alabyshev and Kulakovskaya (who give no data for the pure compounds) show significant variations. In view of these facts, it seemed that an investigation of the electrical conductivities of fused sodium chloride-calcium mixtures would be worthwhile. Apparatus Bridge System—The bridge used,in this investigation is diagrammed in Fig. 1. In general, the elaborations of this bridge over the simple Wheatstone bridge were for the purposes of a) eliminating lead resistances or making them accurately measurable, and b) eliminating major capacitative and inductive effects or balancing them against each other. Lead resistances in the lower arms of the bridge were kept as low as possible by making the leads short and of low resistance wire. This could not be done in the cell arm of the bridge because of the remoteness of the cell from the other bridge components and because of the high-resistance nickel or chrome1 wires used in the cell. Since maximum sensitivity is attained when the resistances of the four arms of the bridge are equal, 50-O resistors were used in the lower arms of the bridge when fused salt conductivities were being measured, and 1000-O resistors were used when the cell was being calibrated with normal aqueous KCl solution. The cell resistance was of the order of 50 ohms with fused salts and of the order of 1000 ohms with normal aqueous KC1 solution. The resistors used were non-inductive and accurate to 50.05 pct (General Radio Co. Types 500-C and 500-H). The lead resistance between point A in the cell and point E at the measuring resistor was eliminated by using the kelvin bridge principle; that is, the voltape drop across the lead from point A to point E was divided between the cell arm of the bridge and the measuring arm of the bridge in proporation to the resistaxes in the lower arms of the bridge.

Jan 1, 1958

By J. Campbell

Various models are discussed for the evaluation of the negative pressures which may occur in solidifying materials which exhibit various deformation modes: elastic-plastic, Bingham, viscous, or creep flow. The inadequacy of the previously proposed elastic-plastic solution for solidifying metals is revealed by comparison with the more reliable creep results which are given graphically for aluminum, copper, nickel, and iron. The maximum tensions experienced in the liquid phase of solidifying spheres ranging in size from large castings to submicron powders are in the range from —10' to —105 atm for these metals. THERE has been much recent interest in the negative pressures associated with the volume change on solidification and in the possibility of the occurrence of cavitation. Considering the freezing of a highly supercooled liquid, an attempt to evaluate the stresses in the liquid ahead of the rapidly moving solidification front has been made by Horvay1 on a microscale and by Glicksman2 on a macroscale. In a casting of a wide freezing range alloy, the pressure differential due to viscous flow of residual liquid through the pasty zone has been discussed by Piwonka and Flemings,3 In a previous publication4 the author has attempted to estimate the negative pressure occurring in the residual liquid of a spherical casting, employing an elastic-plastic model to describe the collapse of the solidified shell under the internal tension. An earlier model assuming a rigid shell was shown to be inaccurate by many orders of magnitude. The elastic-plastic model is critically reviewed here, and other models are developed which are thought to be more closely related to metals and other materials near their melting points. The spherical geometry (Fig. 1) is chosen because the highest shrinkage pressures would be developed, although the analyses are readily adaptable to cylindrical geometry. A parallel sided casting experiences little internal tension because of the relatively easy dishing inward of the sides. (This commonly observed phenomenon has previously been attributed solely to atmospheric pressure.) Furthermore, small regions of confined liquid in a large solidified volume of a casting approximate reasonably well to spherical geometry. ELASTIC-PLASTIC MODEL The author has shown4 that as solidification proceeds the internal hydrostatic tension builds up until the elastic limit of the shell is exceeded. At this point the internal pressure is closely -2Y/3. Subsequently a plastic zone spreads from the inner surface toward the outer surface of the shell. When the whole casting is deforming plastically a rather more generalized analysis taking account of the externally applied pressure PA + 2y/b gives the internal pressure as: P = Pa + 2y/a + 2ys/b - 2 Y In(b/a) [1] The 2y/a and 2ys/b terms result from the tendency of the liquid-solid and solid-vapor interfaces to shrink, reducing their energy, and thereby helping to collapse the solid phase and compress the liquid phase. The 2y/b term would be important only for powders. The last term arises because of the plastic restraint of the solid, resisting collapse and so effectively expanding the residual liquid. From Eq. [I] it is easily shown that there is a minimum in the pressure at the radius amia= y/Y [2] which is of the order of 103K for the metals aluminum, copper, and iron, and corresponds to the minimum pressure Pmin = 2 Y[l-ln(bY/y [3] The results of a fully worked out elastic-plastic solution are given in a previous reporL4 The main criticism which may be leveled at this analysis when applied to metals at their melting points is the strong dependence of the yield stress on the strain rate. The strain rate varies with both solidification conditions (e.g., whether chill-cast or slowly cooled) and during solidification, as is indicated in the following section. Thus an appropriate choice of Y is very arbitrary. Before proceeding to a discussion of models which are strain-rate-dependent, it is necessary to evaluate the strain rate as a function of the rate of solidification. SOLIDIFICATION RATE Various empirical relations have been deduced5 for the rate of thickening of the solid shell by pour- out tests on partially solidified spheres. These, however, are unsatisfactory for our purposes since they become very inaccurate when the liquid core is very small. A theoretical approach is therefore necessary, and some solutions are set out below. Making the assumptions of constant surface temperature of the casting during freezing, no superheat, and a material freezing at a single temperature, Adams8 deduces the approximate solution: which becomes when b » a: Employing a semiempirical approach vallet6 finds:

Jan 1, 1969

By V. A. Josendal, J. W. Wilson, B. B. Sandiford

Two radioactive tracers have been tested as a means of determining core saturation in multiphase flow studies. Cesium chloride was tried as a water-phase tracer, but complications in its use in low permeability cores resulted from sorption of cesium by the core or water-wet pads. IodoI3'ben-zene proved very satisfactory as an oil-phase tracer. The synthesis of iodobenzene from the sodium iodide as received from Oak Ridge is simple and direct. The tracer is insoluble in water and there was no evidence of sorption by any of the core materials used. use of the method to determine saturation profiles during capillary and dynamic desaturations and relative permeability measurements on oil-water and oil-gas systems is described. Comparisons of the dynamic and capillary methods of relative permeability determination were made using the tracer to check core saturation and saturation distribution. Other experiments are also described in which mobility of the oil phase at various saturations was measured by displacing labeled oil by flowing inactive oil. Similar experiments were made using water labeled with cesium 134. INTRODUCTION To be fundamentally sound. any laboratory method of determining relative permeability must meet, among others, the following requirements: (1) the core saturation between the pressure taps must be uniform, and (2) there must be uniform pressure difference between the phases in the region between the pressure taps. In practice it may eventually be shown that appreciable departure from either or both of these conditions may be permitted without introducing sensible error. but the magnitude of such error remains to be established. There is need then for methods of saturation determina- tion which will determine the saturation profile in a core as well as the overall average saturation given by the gravimetric or material balance methods usually employed. Methods which have received consideration include resistivity, X-ray absorption, gamma ray absorption, neutron diffraction, and radioactive tracers. The resistivity method has use in the determination of profile, but needs checking by independent means.' The X-ray method has been used successfully, but requires elaborate equipment and calibration.23 4 At present gamma ray absorption is practical only for very large cores. The neutron methodo does not appear adaptable to measurement of saturation variations in short cores since it is a scattering method. Russell, Morgan and Muskat' employed radiovanadium in a study of the mobility of interstitial water. Coomber and Tiratsook used radioiodine as an oil-phase tracer and measured profiles in unconsolidated sand packs. ADVANTAGES OF RADIOACTIVITY METHOD A thorough discussion of the theory of radioactive tracers and the technique of using them to study the movement of fluids in sands is given by Coomber and Tiratsoos and need not be detailed here. The method requires less equipment than the X-ray method; the counting problem is similar, but the generation and regulation of the radiation, which is a major problem in the X-ray method, is not required in the radioactivity method. In the X-ray method it is customary to add up to 20 per cent of absorber, usually an iodine compound, to the phase to be labeled. while in the radioactivity method a mere trace is sufficient. A possible disadvantage of the radioactivity method is that a disproportionate amount of the activity comes from the portion of the core nearest the counter, whereas the X-ray gives a true average saturation in the region traversed by the beam. 011 the other hand, this characteristic of the radioactivity method renders it peculiarly adaptable to study of certain types of radial variations in saturation. As with the X-ray method, a tracer may be added to either the oil or water-phase. An oil-phase tracer is more generally useful. however. since it permits work on oil and gas in the

Jan 1, 1952

By P. R. Gage, R. W. Bartlett

At high temperatues and reduced oxygen pressuves, molybdenum silicicles oxidize to form SiO(g) vathev than a passivating SiO2 film. This is a sevious problem for low-pressure applications of sili-cide-coated rejvactory tnetals. As oxiclalion pvoceeds, the higher oxidntion potential of silicon initially suppresses oxidation of molybdenum and silicon is depleted near the surface. Eventually, silicon depletion causes secondary passivation (SiO2) mid an active to passiue transition in oxidntion behavior at moderately low pressures. At very low pressures, silicon depletion continues until steady-state oxidation of both silicon and rnolyhdenum can proceed at rates propovtional to their initial stoicliiorrzetvies. Ohsel-vations of 'oxidatiou-rate belzcriliov at temperatures from 1101° to 1700°C and oxygen pressures from 10-7 to 1 at in were made using thermogravimetn'c, X-ray diffraction, and elect?*on-rtric?ro/,vobe techniqrres. The experimental results are in good agreement with calculated lirnits for the various types of behavior that were based on tlievtnochernicnl atzd dffusion rate data for the Mo-Si system. A protective oxide film normally forms during the oxidation of elemental silicon. However, at elevated temperatures and reduced pressures this film is not present and oxidation is rapid. wagnerl has shown that this behavior occurs because SiO(g) is more stable than SiO2. The behavior of the silicides at high temperatures is similar but more complicated. Molybdenum and several silicide compounds are involved and the chemical activity of silicon, or the equivalent silicon vapor pressure, can vary considerably in these phases. Also, diffusion in the silicides resulting from reactions in which a higher silicide is reduced to a lower silicide, or molybdenum containing dissolved silicon, must be considered. EXPERIMENTAL AND ANALYTICAL METHODS Isothermal oxidation experiments were conducted using hot-pressed MoSi2 and Mo5Si3 wafers. Each experiment was conducted at a fixed oxygen pressure by controlling the flow of oxygen in and out of the furnace chamber. Most of the experiments were conducted in a molybdenum-wound tube furnace. Special construction features, including use of a high-purity dense A12O3 refractory tube, permitted operation in high vacuum to 1500°C. Higher temperatures could be obtained at higher working pressures and with a sacrifice of tube lifetime. Temperature was measured with three Pt 6 pct Rh/Pt 30 pct Rh thermocouples and controlled with a proportional controller. Weight changes were monitored with a quartz spring balance. The few experiments, at higher temperatures and low pressures, were conducted in a cold wall vacuum chamber using induction heating with direct susceptance of the sample. Because of the variable levitation effect of the induction coil on the sample, weight changes could not be monitored continuously in these experiments. All samples representing both experimental methods were weighed before and after oxidiation and examined with a microscope and analyzed by X-ray diffraction. The analytical treatment assumes equilibrium at interfaces and uses existing thermodynamic data. For convenience, equilibria are expressed as chemical potentials or as vapor pressures of the gases involved. The resulting differences in equilibrium vapor pressure between adjacent interfaces and between the surface and external atmosphere drive diffusion processes in the solid and gas boundary film, respectively. These diffusion processes govern the rate of oxidation. A bibliography of the sources of thermochemical data for the reactions pertinent to the Mo-Si-O system is given in Table I. Reactions are listed with the sources of free-energy data referenced. Since all of these reactions involve one or more gas species, usually oxygen, a plot of the product-gas chemical potential, -RT In Pg, vs absolute temperature for each reaction is given in Fig. 1. These curves can be used to determine equilibrium vapor pressures or to compare the stability of different compounds in the various gases: O2, Si, SiO, and Moo3,. The data of Table I and Fig. 1 were used to determine the analytical results presented in this paper. EXPERIMENTAL RESULTS The weight changes for three MoSi, samples oxidized at 1500°C are plotted against time in Fig. 2. The treatments were identical except for the indicated variance of oxygen pressure and each curve represents one of three characteristic types of behavior that were observed. The upper curve is an example of passive oxidation, which is defined as

Jan 1, 1965

By T. W. Turk, S. A. Sass

The engineering design features of the Mercur Gold Project crushing, grinding, carbon-in-leach, bullion, reagent, and tailings disposal areas will be discussed in this paper. It presents a project overview and flowsheet along with selected design alternatives. During the engineering phase, major equipment and other features were selected to optimize design within site location and environmental constraints. The project team organization and procedures were adopted to accommodate multiple optimization studies while maintaining a tight engineering schedule.

Jan 1, 1985

By Kyle Wightman

INTRODUCTION CRA Limited is the largest mining group in Australia by value of sales and the second largest company in Australia in terms of share market capitalisation. In the past 25 years, CRA, its predecessors and affiliates have been involved in a number of mining and further processing developments in Australia and elsewhere. Many of these have been financed using project financing techniques. These include Comalco's development of the Weipa bauxite deposits in Northern Queensland in the late 1950's, the Hamersley iron ore developments in the Pilbara region of Western Australia in the mid 1960's, the Queensland Alumina Limited alumina refinery in Gladstone, Queensland, at about the same time, and the Bougainville copper project in 1969/70. In the past three years CRA has again utilised project financing techniques to fund its Tarong steaming coal project in Queensland, the Blair Athol steaming coal project also in that State and CRA's interest in the Argyle diamond project in the Kimberley region of Western Austrlia. PROJECT FINANCE DEFINED Nevitt Definition Nevitt's is the most frequently quoted definition - "A financing of a particular economic unit in which a lender is satisfied to look initially to the cash flows and earnings of the economic unit as the source of funds from which a loan will be repaid and to the assets of the economic unit as collateral for the loan." Risk and Balance Sheet Treatment It is important to focus in more detail on two aspects of project financing, risk and balance sheet treatment. The assessment of the various elements of risk in a project and the sharing of that risk between sponsors and lenders is the most critical feature. At one end of the spectrum is full absorption of risk by the sponsor(s). This can be described as "on risk" or "on credit" or "full recourse" to the sponsor(s) and is effectively a corporate financing. At the other end of the spectrum the lenders absorb the whole risk in a non-recourse financing which is "off risk" or "off credit" for the sponsor. The other aspect is the sponsor's balance sheet treatment. If the balance sheet of the economic unit undertaking the project and the financing need not be consolidated into the balance sheet of the sponsor (because ownership does not exceed 50%) then the financing may be described as off-¬balance sheet. If consolidation is required then the financing is described as on-balance sheet. Most project financings involve some recourse to the sponsor, i.e. they are limited recourse. Very few are non-recourse or off credit to the sponsor. Limited recourse financings may be on-balance sheet although many may also be off-balance sheet insofar as consolidation is concerned. However, sponsor support may very well be a contingent liability to the sponsor and require disclosure by way of note to the balance sheet should consolidation not be required. CORPORATE FINANCE CONTRASTED A financing which is on credit or full recourse to the sponsor, whether it is directly borrowed or guaranteed by that sponsor, is a corporate financing. Lenders will tend to base their credit assessment on a historical assessment of the sponsor's activities and its financial results rather than an assessment of the project or a detailed assessment of the future activities and prospects of the sponsor. PROJECT FINANCE - A BORROWER'S PERCEPTION Although CRA could choose to arrange all finance on a corporate basis (except perhaps for the very largest projects or acquisitions), project financing techniques provide a number of specific advantages which CRA has noted and which should be carefully considered by a project sponsor. Advantages

Jan 1, 1985

By J. L. Huitt, B. B. McGlothlin, J. J. Day

Laboratory tests were made with pure minerals and actual reservoir rock samples to study the effects of hydrothermal (steam m hot water) treatments on reservoir rock properties. These tests showed that hydro-thermal treatment of many reservoir rocks can result in significant rock softening. The softening was attributed primarily to the partial destruction of dolomite and kaolinite and the synthesis of montmorillonite in the presence of excess silica. In many cases, the softening was great enough to cause considerable healing of propped fractures; therefore, a serious reduction in welt productivity could result. In other tests it was found that the addition of ammonia to a hydrothermal treating fluid in a concentration as low as 0.013 Ib/lb of water not only could prevent rock softening but could cause rock hardening. The results of X-ray diflraction analyses of rock samples showed that when ammonia was added to the treating fluid, ammonium-mica and analcite were formed instead of montmorillonite. No significant permeability damage was observed in the sandstones that were subjected to the ammonia-hydro-thermal environment; in some sandstones, permeabifity improvements resulted. INTRODUCTION As the use of steam or hot water becomes more prevalent in well stimulation methods. the need for information on the effects of such treatments on reservoir rock properties becomes increasingly apparent. Several works have been published on high-temperature changes in rock properties,',' but these are more applicable to in situ combustion operations than to steam or hot water injection processes. The mineralogical literature contains many publications which report on the changes occurring with various pure minerals in hydrothermal systems. A review of this literature denotes the ease with which entirely new, crystalline mineral phases can be synthesized from other minerals in hydrothermal environments at temperatures, pressures and residence times typical of those encountered in oilfield thermal recovery or stimulation processes. Discussions of many of these experiments are given by Deer et al. Grim,' Roy et al., Zen\ and Hawkins.' One of the most significant of these pure mineral studies is the hydrothermal synthesis work of Levinson and Vian" in which montmorillonite was synthesized from naturally occurring minerals; i.e., kaolinite, quartz and carbonate minerals (particularly dolomite). These reactions occurred at 575F in only 2 days and at 300F in 5 days. These results may be applicable to petroleum reservoir rocks since the minerals studied were those which are commonly found in sandstones. Furthermore, the environmental conditions imposed in the studies were very similar to those involved in thermal stimulation of petroleum reservoirs, e.g., steam or hot water injection. Other studies have suggested that weak rocks could be hardened by "electrochemical induration", a process in which an electric current is applied to a clay-containing rock body. These tests can be regarded as hydrothermal treatments since they were conducted in some instances with aqueous solutions and since clay temperatures during the electrical treatment reached a maximum of about 100C. Although a number of studies of the reaction of pure minerals have been reported, very little has been published on the reactions of petroleum rock-hydrothermal systems. No work has been reported on preventing the more detrimental rock changes in rock softening which might occur during the injection of steam or hot water into reservoirs. The studies described in this paper were conducted to provide such information. EXPERIMENTAL APPROACH The laboratory tests included studies of the effect of hydrothermal treatment on core samples from several different reservoirs. The hydrothermal treatments (simulated steam treatments) were conducted with distilled water at 575F, for the most part, for periods of 2 to 6 days. This temperature level was selected because it represented that temperature which would probably prevail in several cases under consideration for steam injection projects. The core samples, as well as the pure mineral samples, were contained in high-pressure stainless steel, autoclave-type pressure vessels. The effects of the hydrothermal treatments were evaluated by measuring the penetrometer hardness, formation rock embedment strength and permeabilities of the core samples before and after the treatments (Fig. 1)'" In addition, the mineralogical changes in the specimens were studied by X-ray diffraction. Concomitant with the core sample studies, the mineralogical changes were studied in greater detail by conducting hydrothermal synthesis experiments with pure minerals at similar temperature levels and residence times. For the most part, samples of finely-crushed pure dolomite.

By S. E. Bronisz, R. E. Tate

s-plutonium samples possessing a strong growth texture have been produced by allowing them to transform under pressure from p to a. A fiber texture with [010] parallel to the pressure axis results. The textured samples are expected to be useful in determining the effects of crystallographic orientation on the physical properties of a plutonium, and initial results of measurements of resistivity and mechanical properties are described. THE crystal structure of a plutonium1 is mono-clinic, P21/m, and many of the metal's properties should reflect the crystallographic anisotropy. Unfortunately, it has not yet been possible to grow useful sizes of single crystals of a plutonium. Therefore, few of plutonium's orientation-sensitive properties have been determined as a function of crystallographic orientation. One way to gain information about at least some of the orientation-dependent properties is to study a highly textured sample. Such samples have been produced by cold rolling a plutonium,2 but they are necessarily very small in one dimension. We have now successfully used two other techniques to produce highly textured samples, not limited to small thicknesses. METHODS OF PRODUCING PREFERRED ORIENTATION The texture is produced by causing the plutonium to transform from ß to a while under pressure. It was observed by Gardner3 that applying a compres-sive load during the transformation resulted in the formation of columnar grains of a plutonium, and Cramer4 observed a similar structure in some diffusion couples rolled in the P phase. Neither of these workers, however, investigated the subject beyond these observations. The more flexible of the two methods developed is that of compressive loading. The technique is to enclose a sample of plutonium in a die assembly before applying the load. It is possible, of course, to dispense with the die and simply press the sample between two platens. In this case, however, the unrestrained sample deforms during the pressing, making it difficult to maintain the load and to control the final sample thickness. This compressive loading technique has been used on specimens ranging from 1/4 to 3 in. diameter, with height-to-diameter ratios ranging from 5 : l to 1:6. The procedure begins with loading the sample, a right cylinder of a plutonium, into the pressing die. Plastic deformation of the sample while it is being pressed is minimized by machining the sample so that its diameter is nearly the same as that of the die barrel. Then the loaded die assembly is placed in a vacuum pressing can that fits on a hydraulic press. After a vacuum is achieved the die assembly is heated to 180°C and equilibrated. The load is then applied and the specimen and die are allowed to cool to about 40° to 50°C before the pressure is removed. The resulting sample is composed of rod-shaped a -plutonium grains, the rod axes being parallel to the cylinder axis and the pressing direction. Photomicrographs of the oriented structure are shown in Fig. 1. Although most of the specimen is composed of grains whose rod axes are parallel to the cylinder axis, a thin, peripheral layer consists of rod-shaped grains whose rod axes are perpendicular to the cylinder axis. Presumably, the highly plastic nature of p plutonium leads to approximately hydrostatic conditions during the initial stages of the P — a transformation under pressure. At this time, the grains in the peripheral layer would have grown parallel to the local force direction. During the latter stages of the transformation, the accompanying volume contraction would have eliminated the radial forces, leaving only the axial force and resulting in the growth of the observed structure. The growth texture did not form without the application of pressure. Attempts were made to produce the texture by repeating the standard temperature cycle without

Jan 1, 1965

By R. G. Aspden

The cold rolling and annealing textures were studied for 3 pct Si-Fe grains initially (001) [hkl]. A concentration of (001) [loo] primaries were observed only in the annealing textures of crystals initially having [loo] within 8 deg of the rolling direction. Eke annealing textures of the (001) [I101 cold rolling textures were sensitive to the initial orientation of the grains. Single crystal data were used to explain the formation of (001) [loo] in poly-crystalline malerial. CUBE texture formation in 3 pet Si-Fe sheet occurs during the final high temperature anneal. Its formation is dependent on the proper distribution of (001) plane primaries with reference to the rolling direction&apos; and on the growth of these primaries by secondary recrystallization. The selective driving force for these primaries with (001) within 7 deg of rolling plane is derived from the difference in surface energy between the annealing atmosphere and the crystallographic planes exposed at the surface of the sheet.&apos;-= The alignment of [loo] directions of (001) secondaries with the rolling direction is required for optimum magnetic characteristics7 and is dependent on processing.&apos; A high degree of alignment has been observed when the final cold rolled texture has a strong (111) [ll2] type component3 and the normal grain growth texture prior to secondary recrystallization has components with a [loo] parallel to the rolling direction and planes from (001) to (110) parallel to the rolling plane.1,3,8,9 Generally, this (001) component is much weaker than the (110) component. The growth rate of (001) plane primaries to secondaries has been found to be independent of the orientation of the primaries with reference to the rolling direction, i.e., the secondaries have the same degree of alignment of [loo] directions with the rolling direction as the (001) primaries.&apos; Hence, the rolling and annealing textures of individual grains or single crystals are of interest in understanding the development of the (001) [loo] secondary recrystallization texture. (001) components have been observed in the annealing textures of cold rolled grains initially having a [loo] parallel to the rolling direction and an (001) rotated up to 30 deg from the rolling plane. Crystals initially near the (001) [loo] orientation when rolled under the influence of constraints imposed by neighboring grains form deformation bands and ro- tate in both directions toward (001) <110>.10,11 Deformation bands have been reported also for crystals initially with an (001) within 1 deg of the rolling plane and a [loo] within 1 deg of the rolling direction when rolled as a free single crystal.12 These crystals have weak recrystallization textures and contain near an (001) [loo] component.10-12 When near (001) [loo] crystals are rolled as free single crystals no deformation bands form and the crystals rotate by a single rotation toward (001) [110]. Recrystallization after a 70 pct cold reduction yielded near an (001) [loo] component13 and after a 90 pct cold reduction an (001) [I201 component." Crystals initially near (210) [001] had a texture after a reduction of 70 and 84 pct which was similar to the (111) [li2] but rotated 10 to 15 deg in the transverse direction. These crystals recrystallize to (210) [OOl] or (410) [001] and contain an (001) [loo] component.10,13 An (001) component has not been detected in the normal grain growth textures of other single crystals. Crystals initially having orientations between (110) [001] and (111) [ll2] have a cold rolled texture of principally (111) [ll2] .10>16 Other crystals with a [I101 parallel to the cross direction rotate to (111) [112] and/or (001) [110] stable end orientations. Crystals initially having from (001) [110] to (111) [lie] retain this orientation after cold rolling.15 The cold rolled textures having [I101 directions parallel to the rolling direction had components in the annealing textures related to the deformation textures by 25 to 30 deg rotations about common (1 10) poles. Cold rolled textures of the (111) (112) type recrys-tallized to (120) [001] or (110) [00l]. The purpose of the present work was to further the understanding of the alignment of [loo] directions of (001) secondaries with the rolling direction. The cold rolling and annealing textures of grains initially (001) [hkl] were studied. These data were applied to the formation of (001) [loo] by secondary recrystallization. PROCEDURES AND EXPERIMENTAL TECHNIQUES The (001) poles near the sheet normal and rolling direction are given in Fig. 1 for the 10 grains studied. Each of these grains was located in the center of a polycrystalline specimen approximately 25 mm wide and 50 mm long. The lower case lettered grains, a through dl were about 1.2 mm in diam and near the (001) [loo] orientation. Specimens containing these grains were from a commercial 3 pct Si-Fe alloy with the principle orientation of (110) [001] as obtained by impurity inhibition of growth with manganese sulfide inclusions.17,18 Upper case lettered grains, A through F, were about 6 mm in diam and had (001) planes near the rolling plane and [hkl] di-

Jan 1, 1963

By W. W. Stephens, W. J. Kroll, H. P. Holmes

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,&apos; was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made

Jan 1, 1951

T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—Mr. Killian is to be commended for his inquiry as to why a decrease of 15.3 pct in coke consumption was accompanied by a decrease of only 1.9 pct in the CO/CO, ratio of the top gas. Although I encouraged him in his efforts to find a more significant and meaningful carbon-gas ratio, the method, calculations, and conclusions originated entirely with the author. Whether we agree entirely with the assumptions underlying his corrected ratio, I think we can all agree that a better ratio is needed, and that he deserves credit for recognizing the need and for doing something about it. To be most useful, the CO/CO, ratio for the top gas should reflect the way in which the carbon is gasified in the furnace, particularly the degree of oxidation and the extent of heat release. The effect of CO, from the decomposition of the limestone and the effect of the reaction of CO and water vapor in the upper part of the furnace on the quality of top gas should be isolated from the effect of more basic reactions such as ore reduction and solution loss. The reduction of sufficient iron oxide to produce a ton of pig iron and the accompanying changes in the proportions of the carbon gases can be expressed on a mol basis as follows: 16.5FeA + 16.5CO - 33FeO + 16.5CO, [1] 33FeO + 33.0CO = 33Fe + 33CO. [2] The CO, from eq 1 normally escapes from the furnace because it does not react with coke at the temperature of its release. However, as much as 50 pct of the CO, from eq 2 may react with coke because it is released at temperatures above 1000°C: 16.5CO. + 16.5CO2 = 33CO [3] Thus we see that the gasification of 16.5 mols or about 200 lb of C in solution loss will regenerate as much CO as is required for the last stage of reduction. The pronounced effect of reaction 3 on the final proportions of CO and CO, in the gas stream is obvious. It also follows that reaction 3 materially alters the heat release but it cannot be entirely eliminated in Lake ore practice. A previous study indicates that 100 lb of solution loss may be necessary to maintain the reducing power of the gas. A reduction of 100 lb from the normal level of 200 lb would mean that over 1,-000,000 additional Btu are released in the process. The 100 lb of additional carbon which will be burned at the tuyeres will release 437,000 Btu and the absorption of 583,000 Btu by eq 3 would be prevented. One of the chief objectives of sized ore burdens and more uniform distribution of the gas stream is to minimize solution loss by completing reduction higher in the furnace and in turn to release the maximum amount of heat from the carbon charged. It was odd, indeed, to find that the use of sized ore and sinter in the careful tests reported by Dobscha had changed the CO/CO2 ratio very little. The author has stressed the close correlation between his corrected CO/CO, ratio and production. A correlation of fuel consumption and the CO/CO, might be more logical. Fuel consumption on the prepared ore burden decreased 15.3 pct whereas the corrected CO/CO2 ratio decreased 19.0 pct. Although this agreement between the reduction in fuel and the reduction in corrected CO/CO2 ratio is not as close as the correlation with tonnage, it indicates the corrected ratio is superior to the normal ratio which decreased less than 4 pct. Some adjustment should be made for the reaction: CO + H2O = CO2 + H2 —700Btu [41 because there is evidence to indicate that about one half of the hydrogen is formed in the upper 21 ft of

Jan 1, 1953

By BARONJUPTNER VON JONSTORFF, Andrew A. Blair, GUNNAR DILLNER

IT is a well-known fact that the results of different analysts, when operating on the same identical sample of steel or iron, are far from concordant, and it not infrequently happens that great annoyance and trouble in the commercial community are occasioned by these discrepancies. Attempts have been made at various times to investigate the causes of such differences and to obtain more reliable methods of analysis. The most important of these was made by the British Association in 1889: The following gentlemen, with Sir W. Roberts-Austen as Chairman, and Professor T. Turner as Secretary, were constituted as a committee to investigate the question, viz.: Sir F. A. Abel, Mr. Edward Riley, Mr. G. J. Snelus, Mr. John Spiller, Professor J. W. Langley, and Professor Tilden. Average .samples of steel were prepared in America under the superintendence of Professor J. W. Langley. The steels, in the form of turnings, were divided and distributed to sub-committees in Great Britain, America, France, Germany, and Sweden. In Sweden Professor Åkerman acted as Secretary to the Swedish committee. The Government Department of Tests was appointed in Germany; Mr. Ferd. Gautier in France; the British Association Committee in England; Messrs. William

Mar 1, 1905

By F. E. Jaumot, R. L. Smith

Self-diffusion in zinc has been used as an instrument for comparison of the absorption and sectioning techniques as a means of studying diffusion. Single crystal as well as poly-crystal samples were used asanda the temperature range of diffusion extended from 200° to 415°C. For temperatures above 200°C, the data indicate that the results obtained from the absorption technique agree with those obtained from the sectioning technique. The effect on the values of the diffusion coefficient of electroplating vs evaporation as a means of applying the tracer was investigated and no significant difference observed. It was found that an excess or deficiency of tracer did not materially affect the results obtained from the sectioning technique, but invariably caused errors with the absorption technique. NEARLY all self-diffusion experiments and many alloy diffusion experiments have employed radioisotopes as the instrument for following the diffusion. Of the various techniques in which radioisotopes are applicable, the two most widely used are the sectioning and absorption techniques. In the former, the diffusion coefficient is obtained from a curve of log concentration vs the square of the mean penetration depth. In the latter, the diffusion coefficient is calculated from a knowledge of the decrease in activity at the surface after diffusion. In spite of the importance of knowing the reliability of the diffusion data and the widespread use of these two techniques, they had not been directly compared experimentally on the same samples. Thus, such a comparison was worthwhile. The specific system chosen for this comparison was the self-diffusion of zinc, since the metal was readily obtainable in high purity, single crystals were easily grown, and the anisotropic features of the diffusion added an additional factor of interest to the comparison. Self-diffusion in both single and polycrystals was investigated, since the possibility existed that grain boundaries and grain boundary diffusion might produce different effects for the different techniques. Also, the effects of electroplating vs evaporation as a means of applying the radioactive tracer, and the effects of applying an excess or deficiency of tracer material were studied. The general experimental procedures and the mathematical analyses of both techniques have been described previously in some detail, and only those points essential to an understanding of the present work will be discussed here. The mathematical analysis of the sectioning data requires only a knowledge of the solution of Fick&apos;s equation. where C,, is the initial concentration, C is the concentration at depth x, D is the diffusion coefficient, and p is the absorption coefficient of the solvent metal for the radiation from the solute. Having obtained F from the experiment, the value of z can be read from a plot of F vs In z, and D can then be calculated if is known. The necessity of knowing the absorption coefficient causes most of the criticism of the absorption technique. It is very difficult to measure accurately under the conditions existing in the diffusion experiment, but it is absolutely necessary, as will be indicated briefly later. Portions of this problem have been discussed in detail elsewhere." The difficulties involved in the measurement of the absorption coefficient arise from three principle factors: the physical characteristics of the absorber, the geometry, and complex radiation spectra. The first two are heavily dependent upon the third. If

Jan 1, 1957

By R. W. Smith, K. H. Lee

Bond type simulated closed-circuit grindability tests and batch grindability tests were run on six pure minerals plus a limestone and a taconite ore. The simulated closed-circuit tests were made at five different meshes of grind. The minerals tested varied widely in hardness and breakage pattern. For all simulated closed-circuit tests both Bond and Holmes work indices were calculated and compared. The Bond grindability testlm6 has been widely and quite successfully used for predictions of such items as ball mill power requirements and as an aid in plant comminution equipment selection. The test is interesting in that although run as a series of batch tests it is over-all a simulated closed-circuit test with a circulating load of 250%. The simulated closed-circuit feature is probably the primary reason for the notable success of the test. Perhaps the major criticism that can be brought against the test is that it is time consuming, since it normally takes a trained technician about an eight-hour shift to perform it.4 For many purposes this is an acceptable time requirement. However, if a grindability test is to be used for mill control purposes it should be performed in as short a time interval as possible, preferably under an hour. Sometimes in industry strictly batch tumbling mill tests are run and an attempt is made to correlate such batch tests with plant mill operation. Then an attempt is made to adjust operating tumbling mills based on data from the tests. The tests, however, frequently do not correlate well with operating data. The purpose of the present work was to explore some of the similarities and differences between a simulated closed-circui.t grindability test and a batch type test. Six different minerals plus a limestone and a taconite ore were tested in the experimentation. These materials varied widely in hardness, breakage characteristics, etc. Standard dry Bond grindability tests were mn on all materials at 48, 65, 100, 150 and 200 meshes of grind. Feed material was prepared by stage cmshing to -6 mesh. Initial feed volume was 700 cc. Care was taken to maintain the standard constant weight (about 20125 gm) and number of balls (283) during all the tests. Rotational speed was 70 rpm. Table I lists the materials studied along with pertinent data regarding the materials and Bond grindabilities obtained. In addition, dry batch tests were performed on all materials. These tests were made in the same mill as was used for the Bond tests. An identical ball charge and an identical feed volume were used. After rotating the mill for a predetermined number of revolutions at the same rotational speed as for the Bond test, the material was removed and separated from the ball charge. A screen analysis was performed on this product. Knowing the original size distribution of the feed and the size distribution of the product, it was possible to calculate the grindability or grams of a particular mesh produced per revolution of the mill. After the screen analysis of the product, the various fractions were recombined and placed back in the mill for further grinding. After grinding for additional revolutions of the mill the procedure was repeated. Thus, it was possible to obtain grindabilities for each material at a number of meshes of grind and for various revolutions of the mill. Grind-abilities obtained from batch tests are shown in Table 11. COMPARISON OF BOND AND BATCH GRINDABILITIES Figs. 1A through 1D show relationships between batch and Bond grindabilities. Figs. lA, lB, 1C and 1D show respectively graphs indicating the relationships for batch tests run for 100, 300, 500 and 700 revolutions of the mill. For a particular material on each graph, points are shown for 200, 150, 100, 65, and 48 meshes of grind except for several missing coarse meshes of grind for galena which did not fall conveniently on the figures. For each material and graph the point nearest the origin is for 200 mesh, the next for 150 mesh, the next for 100 mesh, etc. Considering Fig. lA, it is interesting to note that all relationships shown are essentially straight lines. There are, however, considerable differences

Jan 1, 1969