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By J. M. Smith, G. P. Willhite, J. S. Dranoff

Heat transfer rates were measured in sandstones with flow of gases perpendicular to the direction of energy transfer. Effective thermal conductivities ker ranged from 0.7 to 1.7 Btu/(br)(ft)(°F). The contribution of the solid phase appeared to be the most important in these consolidated materials, although the thermal conductivity of the gas had some effect. The velocity of the gas through the pores of the sandstones had no influence upon ker up to values of 168 lb/(br) (sq ft) in agreement with data obtained for unconsolidated beds of glass beads. The present results indicated that gas mixing, and hence heat transfer by convection in the pores, is less for perpendicular transfer of energy than when fluid flow and energy transfer are in the same direction. HEAT TRANSFER PERPENDICULAR TO FLUID FLOW IN POROUS ROCKS Heat transfer in porous media with pore sizes in the micron range depends upon the fluid in the pores and the geometry of the solid phase. The best characterized system is a bed of solid spherical particles. Heat transfer in this system has been studied extensive1y (Ref. 8 summarizes the literature up to 1959) when the pores contain stagnant fluid. When the fluid is in motion the directions of flow and energy transfer have an effect on the heat transfer rates, as demonstrated by comparing the work of Willhite, et al l3 for perpendicular flow and that of Kunii and Smith9 for parallel flow of energy and fluid. For perpendicular flow, no increase in effective thermal conductivity ke was noted up to mass velocities G of 77 lb/(hr) (sq ft). In contrast, for parallel flow ke, increased with G in the same range of flow rates. These higher values of ke in the direction of flow also have been observed3,4,10 in beds of larger particles, 0.1- to 0.5-in. diameter. For beds of consolidated materials, such as porous rocks, data are not available for these compar- isons, although Adivarahan1 reported results for the parallel case. Hence the primary objective of this work was to measure ke values for perpendicular flow of fluid and energy in porous rocks. Of interest also was the variation in effective conductivity with fluid velocity. APPARATUS AND PROCEDURE In the experimental method, a constant heat flux was applied to the inner surface of an annular section of the porous rock. By cooling the outer wall, a temperature gradient through the annular sample was established and measured with thermocouples placed within the sample at various radial positions, and at three elevations (A,B.C). The location of the 2-in. O.D., 3.75-in. long sample in the apparatus is shown in Fig. 1. Fluid entered the bottom (1) of the 3-in. I.D. (approximate) steel shell, flowed upwards through the sample and out at the top (3). pressure taps (2,4) were used to check the permeability of the sample. The energy flowed radially from the centrally-located electric heater through the sample and was absorbed in the water-cooled jacket. The samples studied were naturally occurring sandstones from different locations with the properties given in Table 1. These materials are identical with those used by Adivarahan 1 for the parallel flow of energy and fluid. Prior to use they were refluxed with toluene to remove hydrocarbons and leached with distilled water to remove soluble salts. Each sample was visually examined and discarded if large nonhomogeneities, such as cracks or stone particles, were noted. Eight copper-constantan thermocouples were inserted in holes drilled radially into the sample with

By Anna H. Connard

SUMMARY The discussion focusses on developments in the debt/equity swap market since the Marte project was negotiated in early 1988. It emphasises carrying forward the recent market trends to anticipate the breadth and scope of debt/equity conversions for mine development in the 1990s. Secondary market prices of LDC paper, conversion values and political influences in the host countries and the use of near debt and commodity-based instruments as components of mine financing in debt/equity deals will be placed in the perspective of recent trends and expectations for the future. THE MARTE PROJECT The Marte mine is a gold porphyry deposit in Chile's high Atacama, for which financing was put together at the beginning of 1988. The Marte project was financed by a combination of common equity and loans. It was unusual that the equity infusions were made under different programs. Some of the international equity was infused with fresh funds via DL 600. Other common foreign equity was provided through the conversion of Chilean bank debt under Chapter XIX. On the loan side,. export credits for the import component of machinery and equipment were sought. Local bank financing was negotiated for the remainder of ' the project's anticipated cost. The debt conversion market in Chile was at its apex in terms of interest, activity and government support when the mine financing was arranged. The price of Chilean paper in the secondary market hovered about 62 to 66 cents per U.S. dollar of face value. Meanwhile, the Chilean government was negotiating conversion redemptions significantly closer to full face value. The government differentiated between debt paper exchanged for corporate investors who had sourced that paper in the secondary market, and debt paper held by bank investors who would incur a transaction loss in the conversion. The use of a combined DL 600lChapter XIX equity financing created different yield calculation bases for the various investors. Chapter XIX prevents remittance of profits before year 5 and capital repatriation before year 11. Investors choosing this vehicle have either for a corporate policy in the target project not to declare dividends until repatriation is allowed, or they have to seek uses for the peso liquidity that would be generated through dividend declarations in the early years. However, DL 600 investors face no such waiting period on dividends, nor do they have restrictions imposed on cashing out of the investment before the 11th year. Therefore, any equity structure with components of both investment mechanisms will have inherent differences in cost basis and future income flows for the various participants. This equity imbalance is defensible if the investment motivations of the parties are analyzed: a mining investor using fresh funds looks for a hurdle return on equity calculated at conservative commodity prices, with as much flexibility to reap upside benefits as possible; a mining investor choosing to invest through a debt conversion mechanism will realize a modest short term gain on the conversion, reducing his effective cost basis, but sacrificing some return because of the waiting period on repatriation of dividends. INVESTMENT OBJECTIVES A bank investor exchanging his own paper for an equity participation in a mining project realizes a conversion loss on the transaction. He seeks a risk adjusted acceptable hurdle rate of return to recoup that loss over time. Motivation for the bank investor to take that loss may be derived partly from a strategy to diversify its existing portfolio by internal policy and externally regulated guidelines. The bank will compare yields on its loan portfolio to that country with anticipated dividend flows discounted back at a risk adjusted rate. It will analyze the project with return objectives of yield enhancement over time and with

Jan 1, 1990

By G. C. Wallick, J. S. Aronofsky

This paper presents an experimental verification of numerical solutions of the differential equation describing the transient flow of an ideal gas through a porous material including gas slip effects. Several experiments previously proposed by one of the authors are described together with the correlation of the experimental results with the numerical solutions. Excellent agreement is shown between experiment and theory, thus demonstrating the validity of both the basic assumption made in the derivation of the differential equation and of the numerical solutions of the differential equation. INTRODUCTION In a recent paper,' one of the authors has discussed a numerical solution of the differential equation describing the unsteady flow of an ideal gas through a porous material. This paper was primarily concerned with the effect of gas slip on the flow behavior. In steady state measurements, Klinkenberg2 and others have observed that the apparent gas permeability Kn of a porous material may be expressed as a linear function of the reciprocal average pressure 1/P of the form, ka = b + m/P........(1) where the intercept b is a constant for a given porous material and the slope m is a constant for a given porous material-gas combination. Aronofsky1 assumed that Equation (1) could be used to describe transient flow if P was replaced by the average pressure in an infinitesimal volume element. A number of numerical solutions of the resultant differential equation were presented and specific flow experiments were proposed as a means of testing the numerical solutions. The purpose of the present paper is to describe the results of several of these experiments and the correlation of the experimental data with the results of the numerical analysis. Reference should be made to the previous paper' for details of the mathematical and numerical analysis. EXPERIMENTAL PROCEDURE A simplified schematic drawing of the experimental apparatus is shown in Fig. 1. An 8.89 cm diameter limestone core of length L = 14.82 cm was mounted in a conventional rubber sleeve permeameter cell. The external sleeve pressure in this cell was maintained equal to 500 psig during all experimental tests, thus permitting only longitudinal flow through the core. One end of the core, X = L, was connected to an adjustable cavity of volume V as well as a pressure gauge or manometer. The other end of the core, X = 0, was connected to a Nullmatic pressure regulator which was in turn connected to a nitrogen cylinder or vacuum pump. In each experiment, the core and adjacent dead volume were charged with nitrogen to a uniform gas pressure P1. The pressure at X = 0 was then suddenly raised or lowered to a constant pressure P, and the resulting pressure buildup or pressure decline at X — L was recorded as a function of the time. The porosity + and the permeability constants m and b were determined using the transient method which was suggested by the results of the numerical analysis and which was described in the earlier paper.' The following average values for these constants were obtained as a result of 19 separate evaluations: 171 -0.259 2 0.005 md-atm; b = 0.374 5 0.008 md; and F = 0.098 ± 0.005*. It should be noted that in order that transient phenomena will be slow enough to be observed conveniently, it is desirable to use a porous material of very low permeability, e.g., less than I md. Moreover, it is in this low permeability range that the gas slip effects are most significant. Thus, such a low permeability sample is very suitable for use in an experimental verification of the numerical solutions previously described.

Jan 1, 1955

By H. Margolin, E. Ence

Two versions of the Ti-Mn binary diagram have been published recently.' , -0th diagrams show two compounds in the region between 40 and 70 wt pct Mn, but disagree as to the reaction in which these compounds are involved. The investigation of the manganese-rich portion of the Ti-Mn binary diagram was undertaken at New York University as part of an investigation of ternary systems with titanium and manganese in order to determine which of the proposed diagrams is correct. A number of alloys between 31 and 70 pct Mn were prepared in a manner similar to that described by Cadoff and Nielsen; except that low currents (110 amp in argon atmosphere) and long melting times (up to 20 min) were used to prepare the alloys. Compositions were determined from weight-loss data, assuming all loss as due to manganese. Heat treatments were carried out with relatively large pieces, since there was a tendency for manganese to be lost during heat treatment. When X-ray diffraction data was to be obtained, the central parts of heat-treated specimens were used to make filings or powders which were not heat treated. Specimens were heat treated from the as-cast state. Heat-treatment times were as follows: 1150°C, 1 day; ll00°C, 2 days; 1000°C, 5 days; and 900°C, 15 days. It should be noted that equilibrium was not attained at 900°, 1000°, and in one case, at 1150°C. Metallographic specimens were electrolytically polished and strain etched by a technique described elsewhere.' At least four, and possibly six, phases were found in the region investigated. On the basis of information available at this time, a completely self-consistent diagram cannot be constructed, and therefore data are presented only for those phases which have been identified by both X-ray and microstruc-ture. Of the compounds detected, the one highest in manganese is the Laves phase, TiMn,, which is hexagonal with a MgZn, type of structure.V he diffraction data for TiMn2 from a 70 pct Mn alloy annealed at 1150°C are shown in Table I. The c/a ratio and parameters of TiMn2 agree well with those of Wall-baum hnd Rostoker et al. The values obtained here are c/a = 1.641, a = 4.825A. Another compound is the y-phase which is estimated to contain about 60 pct Mn. The y-phase has a structure which is identical to that of TiMn, with c/a = 1.639, a = 4.906Å. The fact that y has a Laves-type lattice would suggest that TiMn, has a range of solubility which extends from the composition of TiMn2 (69.6 Mn) to that of y (60 pct Mn). However, this could not account for microstructures which, in the 60 to 70 pct Mn region, show several phases in both the as-cast state and after annealing at 1150°C. Fig. 1 shows a two-phase structure of a 60 pct Mn alloy annealed at 1150°C. The phases present are y (white) and e (dark). If y were TiMn, then, according to Rostoker et al.,' the second phase of Fig. 1 should be P-Ti. The diffraction data for the 60 pct Mn alloy of Fig. 1 are shown in Table I. The starred d-values are from the e-phase and these lines do not correspond to those of &Ti. Comparison of as-cast and 1150°C microstructures of the 60 pct Mn alloy indicates that e precipitated from y. Since y has a

Jan 1, 1955

By Peter A. Allen

INTRODUCTION Lac Minerals Ltd., a significant North American producer of gold and other metals for over three decades, recently completed the financing for its third discovery in an eight year period. From 1975 to 1982, three important gold deposits in Quebec and Ontario: namely Bousquet, Doyon and Hemlo, were located and tested by company geologists. When current development plans are complete, Lac will have injected $400 million into these deposits. A discussion of these projects and their financing reveals some extraordinary challenges faced by top mining management. Responses to these challenges developed by Lac management may interest executives planning to proceed with new North American gold or base metal mines. MINE DE BOUSQUET In 1976, we explored a property containing a large low grade surface gold deposit. The geologial setting was exciting and we tested recent rethinking about the volcanigenic genesis of gold and base metal occurrences. These ideas helped pus to persist in drilling a nearby conductor and 600,000 ton, 0.22 ounce/ton orebody was outlined. With gold at $Cdn.150 per ounce the feasibility was approved and work started February 1978. Availability of a company custom mill 35 miles away reduced our immediate capital needs to $8.5 million. First of all, understanding the geological significance of results at Bousquet was critical. Mine and surface exploration geologists at Lac are continually and closely working together to better understand the nature of gold deposits in the Shield. This management emphasis on both pure and mine geology meant that a much larger ore reserve could confidently be predicted. (A proposal to quickly develop and ship the ore to a nearby company mine was discarded.) Instead of designing just for the initial plan of 500 tons per day we therefore included headframe, shaft and hoisting capacity for 1,700 tons and provided a compartment for future shaft deepening. These prebuilt additions were welcomed within two years. The type of collaboration whereby surface and mine geologists make study and field projects of each other's problems sets the foundation for this predictive ability. At Lac, the traditional responsibility for and supervision of the mine geologist by the mine manager is modified by this collaboration. This adds interest and scope to the geologist's work and lets him think beyond production requirements. Besides such management considerations, dedicated, professional geologists with integrity and lots of practical experience are needed to plan successful developments like Bousquet. Second, projecting future bullion revenue was critical and our experience selling production for future delivery gave us a way to ensure that loan repayment at term would not be jeopardized by falling metal prices. Output from a single mine is often reduced or curtailed for numerous reasons, so "selling forward" is done best and with least risk by companies like Lac with more than one or two producing locations for that metal. At first, a forward marketing program was considered unwise, speculative and unorthodox by analysts and other producers. Declining markets in the early 1980s prolonged gold project capital recoveries however, and critics were better able to appreciate the usefulness of such a tool. The notion that gold miners shouldn't sell forward is rooted in the belief that long-run gold prices will rise as modern social theory implementation in democracies inevitably erodes currency values. Selling against this trend goes against this industry belief or "ethic" and is at odds with the company shareholder who expects the gold price to rise not fall. Nonetheless, an efficient tool is available to the gold producer (not to most other metal producers) to quickly disengage from adverse price trends or to lock in spot prices instantaneously for two years or more of profits. Gold had recently retreated from U.S.$200 to $104 and now had reversed to $150. Lac had been forced to close several of its producers during the late 1960s because central bank-controlled

Jan 1, 1985

By R. A. Morse, C. R. Holmgren

The production of oil by water flooding can be substantially increased by the maintenance of free gas saturation in the reservoir during the flooding operation. This effect is accomplished by the alteration of oil relative permeability characteristics and the occupation by gas of pore space that would otherwise be filled with residual oil. The amount of reduction In residual oil can be calculated from appropriate water-oil relative permeability characteristics. This paper presents experimental data in support of the foregoing conclusions and an example of the calculations. The microscopic pore saturation concepts of the mechanism are discussed. A method of practical application to field floods is presented together with discussion of certain limitations. INTRODUCTION The presence of free gas has been reported by a number of investigators to significantly affect the oil recovery which can be obtained from sandstone flow systems by water flooding.1,2,3,4,5 The effect of gas, noted in every instance, has been to cause lower residual oil saturations than could be obtained by water flooding the same systems in the absence of free gas. The degree of improvement in recovery has been observed to vary widely, depending on the systems used and the conditions of the tests. The increased oil recovery obtained because of the presence of gas during a water flood has been variously attributed to changes in physical characteristics of the oil, selective plugging action of the gas, inclusion of oil mist in the free gas phase, and the additional sweeping or driving action of the free gas. All but the first of these suggestions imply changes in the displacement mechanism. The change in viscosity and inter-facial tension of the oil phase, within the pressure range used for all the experimental work, is certainly not sufficient to account for the differences in residual oil saturation noted dess there is a drastic change in the displacement process. One other effect which logically seems capable of causing differences in residual oil saturation of the magnitude noted in the experimental work is that of simple replacement. In a water-wet system containing oil, water, and gas, it is to be expected that the gas will exist inside the oil. This is the position of minimum free surface energy, since the gas-oil interfacial tension will be less than the gas-water interfacial tension. There is no apparent reason to expect that the existence of free gas within the oil phase should alter the saturation at which the non-wetting phase (now oil and gas) should become discontinuous and hence trapped so as to be unrecoverable by direct displacement by water. If this is the situation, then trapping of a certain percentage of gas saturation during water flood should result, at infinite water-oil ratio, in a like reduction of oil saturation below that attainable by flooding in the absence of free gas. It is visualized that the gas will exist as bubbles inside the discontinuous residual oil as illustrated in Fig. 1, with the size of the oil bubbles being substantially unchanged due to the presence of the gas. As a practical matter, it can be anticipated that the presence of a free gas saturation inside the oil phase will reduce the relative permeability to oil which will exist at any particular water saturation. This reduction will be caused by two factors — -the addition of the gas-oil interface, and the reduction of area available for oil flow in the pores containing gas. This reduction in oil permeability at any particular water saturation will result in water breakthrough at a lower water satu-

Jan 1, 1951

By Rex B. McLellan, W. A. Oates, William W. Dunn

Vapor transport experiments have been carried out in order to determine the saturation solubility of carbon in cobalt and nickel with respect to graphite over a large temperature range. Some of the uncertainty existing in the thermodynamics of these systems has been removed and accurate estimates of the heat and entropy of solution of carbon in nickel and cobalt have been deduced. The relatitle partial entropies of carbon are considered to be predominantly vibrational in origin. ALTHOUGH the thermodynamic properties of solid solutions of carbon in cobalt and in nickel have been investigated previously, the results of these investigations show a marked lack of agreement amongst themselves. In this investigation simple vapor transport experiments have been undertaken in order to measure the temperature variation of the saturation solubility of carbon in nickel and cobalt with the object of removing to some degree the uncertainties in the thermodynamics of these systems. In the case of the C-Co system, early measurements of the saturation solubility of graphite in Co show results at the same temperature differing by almost an order of magnitude.1-5 Recently Schenck, Frohberg, and Jaspert6 measured the equilibrium between CH4-H2 mixtures and C-Co solid solutions at five temperatures ranging from 850° to 1050°C. Their values of the activity of carbon in the solid solution, deduced from a knowledge of the chemical potential of carbon atoms in the gas, varies linearly with composition at each temperature and the authors concluded that the solutions were Henryan. The saturation solubilities deduced from Schenck, Frohberg, and Jaspert's measurements are in good agreement with the solubility determined at 1000°C by Rao and Nicholson7 and the value at 1000°C deduced from the measurements of smith8 on the equilibrium between CO/CO2 mixtures and C-Co solutions. The object of this investigation was to check the results of Schenck, Frohberg, and Jaspert and also to extend the range of solubility data to higher temperatures. In the case of the C-Ni system, there is fairly good agreement between the values given by schaefer9 for the saturation solubility of carbon C, in nickel, the value given at 1000°C by Rao and Nicholson,7 and that deduced from Smith's8 measurements of the equilibrium between C-Ni solutions and CO/CO2 mixtures at 1000°C. The values of C, deduced from Schenck, Frohberg, and Jaspert's6 measurements of the carbon activity in nickel are also in fairly good agreement. However, there is a large discrepancy between the above set of measurements and those of Lander, Kern, and Beach," who measured the carbon solubility of nickel in equilibrium with graphite by depositing an excess of graphite on the surface of Ni-foils from a gaseous mixture and subsequently diffusing in the carbon. These results are considerably higher than those mentioned above. The determinations6 of carbon activity a, in nickel from the CH4-H2 equilibrium showed that at all the temperatures investigated, the ac-values varied linearly with concentration up to about a, = 0.6 and then began to increase with concentration much more rapidly. On the basis of auxiliary experiments in which C-Ni solutions were equilibrated with graphite, Schenck, Frohberg, and Jaspert concluded that their CH4-H2 solid equilibrations at high values of a, were spurious and a, behaved linearly with composition up to the saturation limit (a, = 1). The short linear extrapolations of Schenck, Frohberg, and Jaspert's a, data yield values of C, in good agreement with those of Lander, Kern, and Beach." The solubility data for nickel discussed here is presented in Fig. 1 in the form of plots of ln[Cc/(l - 2cc)] vs 1/T. The discrepancies mentioned are clearly seen. In this investigation a vapor transport method is used to measure C, over as wide a temperature range

Jan 1, 1969

By R. M. Asimow

Both smith1 and wells2 have shown that the dif-fusivity of carbon in austenite increases rapidly with increasing carbon concentration. Smith has shown, in addition, that part but not all of this increase can be attributed to the concentration dependence of the activity coefficient of carbon in austenite. From the work of Eshelby', it is known that, because of the image displacements, there is a uniform dilatation of the material in a body containing random centers of dilatation. It is thus tempting to explain the enhanced diffusivity as resulting from this apparent negative pressure caused by the interstitial carbon atoms.* That is, the activation free energy for diffusion is not directly a function of concentration if we consider that the alloy is subjected to a concentration-dependent pressure. To proceed with a quantitative solution, it is necessary to determine the activation volume AV for the diffusion process. An exact calculation of AV is quite a difficult problem and does not appear to have been solved as yet. A simpler procedure is to use the semiempirical, macroscopic theory of seyes' which relates the activation free energy AG to AV. Keyes has shown that for many types of diffusion processes the following relationship is valid Where p is the Gruneisen constant and x the compressibility. This relationship is based on the assumption that AG can be identified with strain-energy terms. In general there will also be contributions to AG due to a change in the energy of the valence electrons of the metal; thus the relation must be considered largely empirical. Surprisingly, for self-diffusion where it is well-known that the electronic contribution is quite important,' the Keyes relation works quite well for many systems. For interstitial diffusion where it might be expected that the relationship is on a firmer theoretical basis, the limited experimental data available is not in particularly good agreement as can be seen from Table I. However, it must be remembered that besides the uncertain basis of the Keyes formula there is considerable uncertainty in some of the experimental values of AV. The only real justification for using the Keyes formula in the present analysis is that it gives a result which satisfactorily solves the problem at hand and, further, there are no more reliable procedures for calculating AV available. The coefficient 3 in Eq. [I] is determined such that the room-temperature value for x is to be used. The activation entropy AS is estimated as 8.95 x 10"3 kcal per OK mole using the values in Table I1 and the Zener" relation AS = PAHIT, where p is a dimensionless thermal coefficient of Young's modulus which is to be evaluated at low values of T/T,, aH is the activation enthalpy, and T, is the melting temperature of the alloy. The resulting value of AG at 1000°C is 25.6 kcal per mole. The Gruneisen constant (p = 3cup/XC,), where p is the density, is evaluated from the room-temperature data in Table I1 after calculating C, from the relation. A value of p = 8.32 g per cu cm based on the value of a. in Table I is used. The result is C, = 5.0 x lo6 erg per g, H = 2.32, and AV = 3.41 cu cm per mole at 1000°C and infinite carbon dilution. It is assumed that the activation volume is not a function of carbon concentration. The theory could be refined to consider AV a function of concentration, but due to the uncertainties in the parameters there seems little justification for this. Carbon dissolved in austenite forms a nonideal solid solution, so that in writing an equation for. the diffusivity of carbon it is necessary to take into account the change in activity coefficient with concentration. The resulting equation is16

Jan 1, 1964

By J. D. Sudbury, J. E. Landers, D. A. Shock

The external corrosion of casing is one of the most important problems facing the present day production man. A 1953 NACE report' estimated the annual cost of casing corrosion at $2,200,000 in 22 fields studied. The fields represented only 10 per cent of the wells in the United States. It was significant that 77 per cent of the failures reported were due to external corrosion. A variety of means for combatting the casing corrosion problem have been discussed in papers such as the NACE survey' mentioned previously. No attempt to revicw these will be made in this paper. Thc scope of this paper has been limited to a discussion of the following major items: (I) an instrument for studying external electrolytic corrosion; (2) use of this instrument to determine the quantity of protective current required to prevent corrosion of casing; and (3) problem of accelerated external corrosion of the oil string at the base of the surface string. ELECTROCHEMICAL MECHANISM OF CORROSION It IS gcncrally belleved that one major cause of external corrosion is the existence of electrolytic cells operating between various formation waters. A theoretical discussion of the role of earth potentials in casing corrosion has been presented by L. de Witte and F. J. Radd.2 A brief picture of the electrolytic corrosion action between two differcnt formations (A and B) is presented in Fig. I. This picture is a review to many but is given to insure clarity. In the anode area, oxidation takes place as iron ions go into solution in formation A as a product of corrosion. In the cathode area. reduction takes place and hydrogen atoms are formed at the boundary between the pipe and formation B. The flow of electrons. as indicated. is into the pipe at the anode or corroding area and out of the pipe into the formation at the cathode. In order to conform with regulations of this journal, the flow of a conventional current (I! is also indicated in this sketch. All subsequent references will be to this so-called conventional current flow and will be indicated by the symbol (I). As this action takes place the layer of hydrogen developed on the cathode offers a resistance to the flow of current in the cell. It is said (hat the cathode has been polarized. This polarizing film can be rcmoved by addition of a so-called dcpolarizing agent which reacts with and removes this hydrogen film. Such an agent must be present in ordcr for this corrosion reaction to go at a rate sufficient to cause a severe corrosion problem. The two common depolarizing agents are: (I) oxy-sen. which readily reacts with hydro gen to form water, and (2) certain bacteria which use atomic hydrogen as part of their life process. It is not difficult to explain the presence of these agents. Oxygen may be present in some very shallow formations. Sulfate reducing bacteria are found to exist in nearly any ground where mud pits might be dug. THE CASING POTENTIAl-PROFILE Instrumentation A sketch of the equipment* uscd in determining casing potential profiles is shown in Fig. 2. The tool is run in the hole using a hoist truck with a three-conductor cable. This tool must be run with tubing and rods out of the hole and should be run with the flow line disconnected. By proper choice of electrode size it can be run in any size casing. The electrodes must be run in an open hole or a hole filled with oil. Measurements cannot be made while immersed in water. The tungsten carbide-tipped knives serve as the electrical robes and arc spaced 25 ft apart. The potential difference along a 25-ft section of casing is measured with a potentinmeter to an accuracy of about 5 mv. Current flowing in the pipe can then

Jan 1, 1956

By R. E. Collins, Paul B. Crawford

Potentiometric model studies have been made of ertically fractured reservoirs. All fractures originated at he well and extended into the reservoir for various distances. Studies were made to determine the areal sweep efficiencies for line-drive patterns. The areal sweep efficiency for the unfractured system studied war 70.6 per cent. It was found that if the vertical fracture war paralIel with the direction of flood, the areal sweep efficiency may be considerably reduced, approaching zero in some instances. If the fracture was at right angles to the direction of flood, the areal sweep efficiency may be greater than that for the unfractured system. The sweep efficiency depends on the length and orientation of the fracture and direction of the flood. It is concluded that considerable effort should be made to determine the nature and direction of fractures before initiating a flooding program. Such information is required if the maximum sweep efficiency is to be obtained and channeling is to be reduced to a minimum. INTRODUCTION The recent development and application of fracturing techniques to petroleum reservoirs has served to focus considerable attention on the effect such fractures may have on secondary oil recoveries. The opinion has been expressed that fracturing may not alter appreciably the water flooding possibilities. Others have thought that channeling may occur and that the creation of fractures may serve to substantially reduce the possibilities of conducting a successful water flood in the reservoir The purpose of this study was to obtain quantitative estimates of the effect of vertical fractures on the areal sweep efficiencies of line-drive flooding patterns. In presenting this work on vertical fractures, it is not to be inferred that the present fracturing techniques result in producing a vertical fracture. The types of fracture which are created are not known with certainty in every case. Some are believed to be horizontal, others inclined along bedding planes, and some data indicate vertical fracturing. Each fracture will probably exert a different influence on the sweep efficiency of the secondary recovery program; consequently each fractured well should perhaps be considered as a separate problem, requiring a careful analysis. Preliminary work on the effect of fractures on producing capacity of a well indicated that for practical purposes many fractures may be treated as having a nearly infinite permeability This assumption appears to be valid in some instances where the permeability of the fracture is only 10 or 100 times greater than the permeability of the matrix. It is known to depend on the type, orientation and length of the fracture. In realization that fractures of only 0.01 in. width have calculated permeabilities near 5,000 darcys, it is believed that many fractures may be considered as of near infinite permeability without incurring serious error. Primarily for this reason this study was made with fracture analogs of very great permeability compared to the matrix. FRACTURED SYSTEM ANALOG The pattern sweep efficiencies reported here were obtained with the aid of a potentiometric model. The application of this type model for solving reservoir problems has been described in the literature.1,2,3 The electrolyte reservoir was 20 in. wide by 30 in. long by approximately % in. deep. The liquid depth was constant, which corresponded to a constant permeability-feet product from the injection to the production well. The electrolyte reservoir was built to correspond to a unit in the line-drive pattern shown in Fig. 1. This figure shows part of an infinite array of wells having alternate rows of fractured and unfractured wells. The area within the dashed rectangle shows the area generally studied in the model. In using the model to represent a fractured system, a thin strip of copper was soldered to the well or wells and the length and orientation of the strip was made to conform to the vertical fracture under consideration.

Jan 1, 1955

By Robert M. Lewis

Can wet-ground mica be produced from mica schist ores, and if so, would its properties be comparable with products now on the market? This was the problem which prompted the development of a flowsheet for the beneficiation of mica schist. The fine-ground mica industry relies on weathered pegmatites and alaskite ores as sources of raw material. The mica concentrates obtained from these ores are relatively clean and require moderate beneficiation to meet color and bulk-density specifications. Mica obtained from mica schist is iron-stained and decrepitated and requires additional beneficiation to produce a wet-ground mica product. Despite these adversities, there are several advantages to be gained by mining and processing mica schist ores. The mica content of these ores is considerably higher than that of the pegmatites and alaskite ores now being mined, often containing in excess of 40% mica. This higher-grade mica feed should promote a lower mining and milling cost. The mica schist ores with their higher mica content would mean less tailings to handle; however, there would have to be a means for disposing of acid and sulfate wastes. A flowsheet was developed whereby mica could be recovered from mica schist ores and beneficiated in a way that would result in a high-quality end product.' The essential phase of the process involves using reducing reagents to increase the magnetic susceptibility of iron contaminants which then can be removed with a magnetic separator. General Treatment Procedure The mica is floated by either of two methods, an amine float in an acid circuit' or the U.S. Bureau of Mines (USBM) amine-fatty acid float in an alkaline circuit' The flotation mica is ground in a pebble mill to liberate contaminated particles and expose iron-stained surfaces. The concentrate is then conditioned with a reducing reagent and passed through a Frantz Ferrofilter for the removal of magnetic material. The nonmagnetic product is acid-leached to further reduce the iron contamination. The leached material is then ground to product size and checked for specifications. Discussion of Flowsheet and Its Development Flotation: The mica is concentrated by flotation using either of two methods: an amine float in an acid circuit, or the USBM amine-fatty acid float in an alkaline circuit.' The writer does not wish to elaborate on the relative merits of the two flotation procedures; however, after investigating ores from various localities, it was felt that the amine float in an acid circuit was more consistent when using a standard procedure. Iron Reduction and Magnetic Separation: This phase of the flowsheet may be considered the key to the process. It was developed when it became apparent that hot acid leaching had just about reached its maximum effective¬ness for color improvement. S. C. Sun and William Hirsh in "Hydrochloric Acid Leaching of Iron From Pennsylvania Aluminous Clays,"` reported iron extraction for -20-mesh minerals of 82.20% for hematite and only 33.46% for magnetite. The test procedure employs a 19% hydrochloric acid solution, 104°C temperature, and 10% solids. It was felt that magnetic removal of some of the iron contaminants before leaching therefore would be advantageous. Since the iron minerals present as contaminants vary in magnetic susceptibility, it was decided to experiment with reducing reagents as a means of influencing their magnetic properties. Zinc hydrosulfite or sodium hydrosulfite were the reagents used throughout the tests. The procedure developed consists of conditioning the mica concentrate in a closed container at approximately 5% solids with a reducing reagent. Approximately 10.0 lb of zinc hydrosulfite per ton of mica concentrate is used. The ferric iron is reduced to the ferrous state (magnetic) and oxidation is retarded by isolation from the atmosphere in a closed container. After the desired conditioning time has elapsed, the material is passed through a Frantz Ferrofilter where the magnetic particles are retained and discarded as

Jan 1, 1972

By R. A. Morse, C. R. Holmgren

The production of oil by water flooding can be substantially increased by the maintenance of free gas saturation in the reservoir during the flooding operation. This effect is accomplished by the alteration of oil relative permeability characteristics and the occupation by gas of pore space that would otherwise be filled with residual oil. The amount of reduction In residual oil can be calculated from appropriate water-oil relative permeability characteristics. This paper presents experimental data in support of the foregoing conclusions and an example of the calculations. The microscopic pore saturation concepts of the mechanism are discussed. A method of practical application to field floods is presented together with discussion of certain limitations. INTRODUCTION The presence of free gas has been reported by a number of investigators to significantly affect the oil recovery which can be obtained from sandstone flow systems by water flooding.1,2,3,4,5 The effect of gas, noted in every instance, has been to cause lower residual oil saturations than could be obtained by water flooding the same systems in the absence of free gas. The degree of improvement in recovery has been observed to vary widely, depending on the systems used and the conditions of the tests. The increased oil recovery obtained because of the presence of gas during a water flood has been variously attributed to changes in physical characteristics of the oil, selective plugging action of the gas, inclusion of oil mist in the free gas phase, and the additional sweeping or driving action of the free gas. All but the first of these suggestions imply changes in the displacement mechanism. The change in viscosity and inter-facial tension of the oil phase, within the pressure range used for all the experimental work, is certainly not sufficient to account for the differences in residual oil saturation noted dess there is a drastic change in the displacement process. One other effect which logically seems capable of causing differences in residual oil saturation of the magnitude noted in the experimental work is that of simple replacement. In a water-wet system containing oil, water, and gas, it is to be expected that the gas will exist inside the oil. This is the position of minimum free surface energy, since the gas-oil interfacial tension will be less than the gas-water interfacial tension. There is no apparent reason to expect that the existence of free gas within the oil phase should alter the saturation at which the non-wetting phase (now oil and gas) should become discontinuous and hence trapped so as to be unrecoverable by direct displacement by water. If this is the situation, then trapping of a certain percentage of gas saturation during water flood should result, at infinite water-oil ratio, in a like reduction of oil saturation below that attainable by flooding in the absence of free gas. It is visualized that the gas will exist as bubbles inside the discontinuous residual oil as illustrated in Fig. 1, with the size of the oil bubbles being substantially unchanged due to the presence of the gas. As a practical matter, it can be anticipated that the presence of a free gas saturation inside the oil phase will reduce the relative permeability to oil which will exist at any particular water saturation. This reduction will be caused by two factors — -the addition of the gas-oil interface, and the reduction of area available for oil flow in the pores containing gas. This reduction in oil permeability at any particular water saturation will result in water breakthrough at a lower water satu-

Jan 1, 1951

By G. R. Countryman, G. H. Thomas, I. Fatt

Procedures are described for scaling up turbulent friction pressure drops of inelastic fluids and laminar friction pressure drops of inelastic/elastic fluids in circular ducts. The laminar scale-up calculation method does not require the use of arbitrarily defined flow models, and can be performed directly from laminar capillary viscometry data, or by means of a numerical solution of the integral equation for Poiseuille flow, inputing true shear rate-shearing stress data from other simple shearing experiments. e.g. Couette and plane Poiseuille flows. The turbulent scale up procedure, based on the Dodge-Metzner correlation for inelastic fluids, requires evaluating the characteristic rheological parameters at the existing wall stress under laminar flow conditions. Since the wall stress is the quantity sought in a pipe flow scale-up problem, a trial-and-err or solution is indicated, and therefore a calculation method has been developed and programmed for a medium-size magnetic-drum-memory digital computer. Laminar flow data from other somces may also be adapted to this turbulent scale-upmetbod for inelastic fluids. Comparisons between predicted and experimentally observed friction losses for generalized Reynolds numbers ranging from 3 — 32.000 indicate an error band width of less than 10 per cent in circular tubes ranging in size from 0.5 to 1.89 in. in diameter. INTRODUCTION Considerable effort has been devoted to the problem of establishing an accurate procedure for predicting the laminar and turbulent flow behavior of non-Newtonian materials in pipes from data obtained with small scale laboratory or pilot plant equipment, as evidenced by the variety of reviews on the subject.1-3 Although there does not appear to be a universally accepted scale-up method for laminar flow, the various methods currently employed can be divided into two principal categories depending upon whether a functional relationship between shear rate and shearing stress is assumed, or whether a generalized correlation is adopted. The methods of Hedstrom4 and of Weltmann are typical of the first category, while the generalized correlation of Metzner and Reed6 illustrates the second category. Under appropriate conditions either approach yields a reasonably satisfactory description of laminar flow behavior. In contrast, the prediction of non-Newtonian transitional and turbulent friction losses is much more complex. For example, certain types of materials have been observed to sustain laminar flow at much higher flow rates than Newtonian liquids. When turbulence does develop, the level of agitation is damped to such an extent that the friction factor is lower than that of the original low viscosity Newtonian medium. Extremely broad transition regions and "diameter effects" have also been noted in the turbulent flow of certain chemically complex materials.' Aside from the latter complications, which are attributed in part to viscoelasticity, the existence of a variety of scale-up procedures for predicting transitional and turbulent friction losses is due principally to the chioce of viscosity parameter used in the definition of the Reynolds number. In contrast, Dodge and Metzner have demonstrated that the friction factorReynolds number relationship for inelastic fluids can be satisfactorily generalized provided the fluid property parameters are evaluated at the existing wall shearing stress.* However, the quantity usually sought in a pipe flow scale-up problem is the wall stress, and hence a trial-and-error procedure is required when dealing with non-power law materials. In this report we discuss two calculation methods: (1) for determining the wall stress, and hence the friction pressure drop, for inelastic fluids under conditions of turbulent flow by means of an iterative procedure, and (2) for predicting laminar friction pressure drops without recourse to arbitrarily defined flow models.

By Robert E. Brand, Strathmore R. B. Cooke

For a study of the bonding that occurs in magnetite pellets during oxidation, cubes of magnetite, hematite, and quartz were prepared, each with one surface polished and nearly optically plane. These faces were fired together under pressure and at various temperatures to determine whether bonding would occur. Sections of surfaces that bonded were examined microscopically. An attempt was made to measure the strength effected by this treatment. EARLIER work1,2 has shown that the strength developed by fired magnetite pellets containing silica or silicates is due to three separate effects. Two of these are associated with the formation of slag in the interior of each pellet at temperatures above 1000°C, where the atmosphere is substantially though temporarily neutral. The third is independent of the silica content and is responsible for the development of a hard shell around the pellet during the initial stages of firing, a condition which permits the pellet to assume the increasing load of the overlying burden and prevents extrusion of the slagged and semi-liquid interior. Pellets made from hematite concentrates do not show these effects unless specific additives are incorporated, and it is these differences in behavior which in large part account for the difficulty in producing satisfactory pellets from such concentrates. Elsewhere it has been stated that "the most important factor responsible for the development of strength in fired magnetite pellets containing no additive is the oxidation of magnetite to hematite and the subsequent recrystallization and grain growth of this constituent."' The object of the investigation reported in the present paper was to study in detail the mechanism described above and to evaluate its contribution to the strength of the fired pellet compared with other possible mechanisms, excluding slag bonding. This was effected by placing together polished faces of two cubes prepared from specific minerals and then heating them under constant pressure at different temperatures both in air and in nitrogen. The materials used were magnetite, hematite, and quartz. The magnetite was coarsely crystalline material from western Montana, the hematite was Itabira ore from Brazil, and the quartz was of optical grade but of unknown origin. A high-grade Lebanon (Pennsylvania) magnetite concentrate was used to prepare briquets for the investigation of bonding strength. Analyses of the iron oxide materials are given in Table I. The specimens for furnace treatment were prepared with a carborundum cut-off wheel, which cut the minerals into cubes approximating % in. along each edge. Care was taken to make the sides as parallel as possible. The edges of the faces to be polished were beveled, and the cubes were mounted in brass rings with sealing wax, this being essential to prevent the specimens from rocking during polishing. To prevent excessive friction, the wax was recessed so that only the brass ring and the face of each specimen would be in contact with the polishing lap. Each specimen was then ground with No. 600 carborundum to produce a level surface before polishing. The Graton-Vanderwilt process was not used for polishing because of the long time required by this method, but several other methods were tried. Cloth laps using levigated alumina or chromium oxide did not produce the desired polish. Satisfactory results were obtained by means of a pitch lap: which was used for all the mineral cubes, with levigated alumina as the polishing medium. The lap was operated in a machine similar to those used in the preparation of single optical surfaces. It was run at low speeds and moderate pressures, and polishing was stopped occasionally to prevent overheating of the lap. A good polish with flat surfaces could be obtained in about 5 min. After polishing the sealing wax was removed either in hot water or in a solvent such as turpentine.

Jan 1, 1955

By L. A. Wood, A. G. Winslow

Subsidence has occurred in several areas of the upper Gulf Coast region of Texas, although in most cases this is not evident without precise instrumental leveling. As referred to in this report, the region comprises about 7200 sq miles of the Gulf Coastal Plain and includes all or parts of the following counties: Harris, Fort Bend, Waller, Brazoria, Galveston, Liberty, Chambers, Orange, and Jefferson (Fig. 1). Topographic relief is low, ranging from sea level at the Gulf of Mexico to 300 ft or more in northwestern Harris County. In this upper Gulf Coast region, which embraces the most heavily populated and industrialized parts of Texas, industrial and municipal water supply is obtained chiefly from wells. Largest center of ground-water withdrawal is the Houston-Baytown area, where about 200 million gallons per day was pumped in 1956 for municipal and industrial use. Other large centers of ground-water withdrawal include the Alta Loma sector and the heavily industrialized Texas City area in Galveston County, where about 23 mgd was pumped in 1956. In the Freeport area in Brazoria County about 6 mgd was pumped in 1956 for city and industrial supply. In addition to withdrawals in metropolitan districts, great quantities of ground water are supplied by irrigation wells to thousands of acres of rice. These wells are widely dispersed over many miles, principally in Harris, Waller, Fort Bend, Brazoria, and Liberty counties, and effects of pumping are not so readily noticed as in the industrial and metropolitan sectors. Subsidence: Starting with the 1905-1906 line from Smithville, Tex., to Galveston, the U. S. Coast and Geodetic Survey has extended a network of first and second-order level lines throughout the upper Gulf Coast region. In 1918, when a line was run from Sinton, Tex., to New Orleans, La., a tie was made to the 1905 leveling at Houston. In 1932-1933 a line was run from Palestine, Tex., to Houston, and a good deal of leveling was carried out in the vicinity of Houston. At this time the entire network was adjusted to the Sea Level Datum of 1929. In 1935-1936 and 1942-1943 several new lines were run and considerable releveling was performed. Supplementary adjustments were made after both the 1936 and 1943 levelings in order to reduce the elevations to the Sea Level Datum of 1929. These adjustments probably masked some of the subsidence that had occurred up to that time, although a certain amount of subsidence was noticed in the 1943 leveling. When several lines in the vicinity of Houston and Galveston were releveled in 1951, the regional nature of the subsidence became apparent.' Direct comparison with the 1943 leveling was possible because the datum was not changed. Comparisons with prior leveling were unreliable because of differences in the early and subsequent datums. In 1953-1954 many lines in the region were re-leveled and in 1957 the entire network, including the elevations previously determined, was readjusted to determine the changes in elevations as indicated by various levelings between 1905 and 1953-1954. In this instance the adjusted elevations were held fixed near the boundaries of the region where the bench marks seem to have remained stable. The only sea-level connection held fixed was the connection of the 1905 leveling to the 1903-1906 tidal series at Galveston. Almost the entire region has been at least slightly affected by the subsidence, some areas to a great extent. The profiles of subsidence (Fig. 2) and the map showing the contours (Fig. 3) illustrate both regional and local changes. A large area of subsidence is centered in the Houston-Baytown district, where the maximum recorded is about 2.7 ft between 1905 and 1954. This probably falls short of the actual maximum, since land surface subsided as much as 2.5 ft in the industrial section alone between 1943 and 1954. Sub-

Jan 1, 1960

By C. B. Alcock, R. G. Hudson

Sulfur pressure measurements above FeS in equilibrium with iron have been carried out by the Knudsen orifice method. A comparison is made of the weight loss of the cell per unit time obtained in the above experiments, that calculated from Richardson and Alcock's measurements of the S2 pressure above FeS in equilibrium with iron, and the dissociation constant for diatomic sulfur from spectroscopic and thermal data. EXTENSIVE equilibrium measurements have been made to determine the sulfur potentials of a great many systems of metallurgical interest.' In order to confirm their reliability, to supply data which may be of use in further thermodynamic calculations, and to establish the reliability of the Knudsen orifice in obtaining accurate thermodynamic values at high temperatures, the present investigation on the pressure of the gaseous species above FeS in equilibrium with iron has been carried out. The Knudsen orifice method has been used for these pressure measurements. Experimental The apparatus and general technique for this investigation are the same as that reported for the determination of the vapor pressure of silver.' To reduce the residual gas pressure in the evacuated chamber, a titanium getter, maintained at run temperature, was introducbed. Several types of Knudsen cells were used—platinum, zircon, and fused silica. The orifice in the zircon cell was fashioned with a small diamond wheel. The same precautions were used in this investigation as were employed in the work on Mo2S2.3 The FeS-Fe mixture was prepared by heating a sample of pure FeS,, supplied by K. K. Kelley of the Bureau of Mines, with excess iron powder, cp grade, obtained from the Fisher Scientific Co. These two substances were heated in a closed Armco iron crucible at 960°C, held in a vacuum of less than 10" mm Hg for 24 hr. The mass was then removed from the cell and ground in an agate mortar. In this form it was charged to the various Knudsen cells. Heating the Knudsen cell for an additional two days was sufficient to obtain constant rates of weight loss of the cell. The data obtained in this investigation are recorded in Table I. To establish whether or not a sulfide of iron is volatile at these temperatures, 0.7646 g of the FeS-Fe mixture, described above and containing 69.2 pet Fe, was placed in the zircon Knudsen cell. Run Nos. 103 to 109 were performed on it. After the completion of these runs, the total amount of iron left in the cell was obtained by chemical analysis. It contained 0.537 g Fe, compared to 0.529 g in the original charge. Thus, there was an apparent gain in iron of 1.5 pet. This is attributed to unknown experimental error, and the conclusion is that no sulfide of iron is volatile. The vapor pressure of pure iron4 is about one thousandth that of the sulfur pressure' at these temperatures. The vapor pressure of iron inside the Knudsen cell will be almost exactly that of pure iron, since in the iron-rich phase the percentage of sulfur is of the order of 0.025 pet.At this low percentage of sulfur Henry's law is probably obeyed by the sulfur. Thus, the iron will obey Raoult's law. In any event, the vapor pressure of iron will be lower than that of pure iron and, since the vapor pressure of pure iron is negligible compared to the pressure of sulfur, the weight loss of the cell due to the vaporization of iron should be negligible. Since neither iron nor FeS is volatile to an appreciable extent, the total weight loss of the cell must be due to the vaporization of sulfur. Discussion and Calculations On the assumption that S, is the only gaseous species present in appreciable quantity, its pressure

Jan 1, 1957

By C. R. Masson, M. L. Pearce

The nitrogen contents of seven specimens of iron and steel were determined by the three methods. Good agreement won generally observed between the results of the isotope -dilution and Kjeldahl determinations, tltzts establishing the reliability of the isotope -dilutzon technique. For some specimens, the vacuum-fusion values at 1650 °C were lower than the corresponding Kjeldahl values by up to 0.0015 pct absolute. These differences were eliminated for a specimen of "pure" iron by performing the vacuum-fusion analyses at 2100 ° to 2240 °C. The reason for this relatively high temperature required m the vaczium-fusion analyses is discussed. ThE determination of nitrogen in iron and steel has been the subject of numerous investigations and a concise review of the extensive literature in this field has recently appeared.' Two methods of analysis are most commonly employed, the vacuum -fusion and the chemical or Kjeldahl method. Except in special cases where the presence of certain alloying elements may present difficulties, both methods are generally regarded as applicable, although the vacuum-fusion method is more sensitive and is often preferred for samples of very low-nitrogen content. The method of isotope dilution, first employed for the determination of gases in metals by Kirshenbaum and Grosse,2 has recently been applied to the determination of nitrogen in iron and steel.3,4 The method is attractive in that it does not require the quantitative extraction of gas from the metal specimen. Staley and Svec3 modified the standard Kjeldahlpro-cedure by introducing, along with the steel sample, a measured amount of ammonium sulfate enriched in the isotope 15N. The nitrogen content was obtained by measuring the isotopic ratio 15N/14N in the resultant solution. The technique involved the distillation of nitrogen as ammonia from alkaline solution and subsequent oxidation of NH4+ in the distillate to gaseous nitrogen. The results for iron and steel samples of commercial origin were often in reasonable agreement with values quoted by the suppliers, although occasional marked discrepancies were observed, particularly with the results of vacuum-fusion analyses. Preliminary work in this laboratory4 on the determination of nitrogen by isotope-dilution in the gas phase yielded results for three samples which were significantly higher than the values obtained by vacuum-fusion. The present paper describes an extension of this work to a wider variety of samples. Analytical results by the Kjeldahl method are also reported. EXPERIMENTAL The technique employed for the isotope-dilution determinations was similar to that described elsewhere.4 Several minor modifications were made to the apparatus. These included the use of molybdenum instead of platinum-rhodium suspending wires when crucibles were degassed at temperatures above 1600°C. The circulatory system used previously for converting CO to CO2 was replaced by a single chamber, the walls of which were cooled directly in liquid nitrogen. Temperatures were measured with an optical pyrometer which had been recently calibrated and, as in the previous study, were minimum values obtained by sighting on the center bottom of the crucible. Temperatures obtained by sighting on the interior walls were always higher by 100' to 130°C with the design of crucible employed. Flat-bottomed crucibles exhibited an even larger temperature difference. To check the efficiency with which crucibles were degassed in the isotope-dilution apparatus, several experiments were done in the vacuum-fusion apparatus, suitably modified4 for isotope-dilution studies. Faster pumping speeds and higher degassing temperatures were possible, the latter due to the use of a generator with a higher power output (10 Kva at 398 kc per sec). In these experiments the combustion of CO was omitted and a correction4 was made for the contribution of CO to the ion current at m/e 28, used in determining the isotopic ratio R = l5NP4N. This correction did not seriously influence the re-

Jan 1, 1962

By Gordon H. Geiger, John M. Svoboda

One mechanism of metal penetration into mold aggregates by cast steels is vapor state mass transport. In order to further understand and quantify this mechanism, the steady-state diffusion of metallic vapors was studied at 1250" to 1600°C in controlled oxygen pressure atmospheres by measuring the weight loss from a metal bath whose vapors were allowed to diffuse through a porous aggregate compact held at constant temperature. Mass transport rates substantially greater than those predicted from the assumption that the vaporizing species was the elemental metal vapor were observed. Vaporization rates were found to increase with an increase in the oxygen partial pressure in the gas atmosphere with maximum vaporization occurring at oxygen partial pressures just below those in equilibrium with a liquid oxide layer at the given temperature. When the liquid oxide layer was present, no vaporization was observed. Metal carbonyls were ruled out as the vapor species involved because of their thermodynamic properties. The species with the enhanced volatility were deduced to be gaseous metal-oxygen molecules, probably the polynuclear oxides (FeO)2 and (Mn0)2. Diffusion followed the ordinary diffusion mode, and Knudsen diffusion is not important in normal foundry molds. The interdiffusivities of the metallic vapors and the mold atmosphere, through the porous aggregates, were measured. The effective interdif-fusivity of the vapor species and mold atmosphere through the aggregate may be expressed as follows: Deff,12 - — where E is the void fraction of the aggregate and 7 is the "tortuosity factor". Aggregate material had no effect on diffusion rates, and the only relevant parameter was the void fraction. Values for 7 ranged from 3 to 6 for normal foundry aggregates with 4 being considered a good representative value. An area of interest in high-temperature metallurgical processes which has received little attention in the past is the diffusion of metal vapor species in porous aggregates. Research into the metal penetration phenomenon' in foundry molds has shown that a major penetration mechanism is the vapor transport of metallic species into the porous foundry sand molds, followed by condensation of metallic films on the sand grains. Considerable study of the vaporization of metallic species has been reported in the literature, and the vapor transport properties of many metallic species have been determined.2'3 Many instances have been observed where the vaporization behavior could only be explained by the existence of a metallic species with a vapor pressure greater than the elemental metallic species. These species were identified or, in some cases, presumed to be carbonyls,4,5 hydroxides,6-9 or vaporous oxides.10-16 The diffusion of gases through porous aggregates has received considerable attention in the literature pertaining to catalysis, although primarily at low temperature, and more recently in the literature concerned with ore reduction.17-22 The following experiments were devised and carried out in order to determine the nature of the metallic species involved in the metal penetration phenomenon, and the effective diffusivities involved. EXPERIMENTAL APPROACH Steady-state diffusion was selected for experimental convenience. The experimental systems used, shown in Figs. 1 and 2, consisted of a porous aggregate specimen contained in an impermeable alumina tube held above, and just separate from a metal bath. The entire system was held at constant temperature and pressure in a furnace with a controlled oxygen partial pressure atmosphere. After a brief period of nonsteady state behavior, a steady flux of metal vapor through the porous aggregate will develop due to the concentration gradient of metallic vapor in the gas phase. The flux of metallic vapor from pressure may be neglected because there is no pressure gradient. There is no flux from convection because there is no net flow of gas within the metal-aggregate system, and thermal diffusion is negligible compared to the flux from ordinary diffusion. If the material being studied is allowed to vaporize until steady-state behavior is attained, the experimental results may be analyzed using Fick's First Law.

Jan 1, 1970

By F. A. Crossley

The additions: o, Sn, Zr, Cb, Mo, and V were studied for their effects on the a/a + Ti3A1 boundary of Ti-A1 base ternary alloys. These additions were chosen because of their importance to commercial titanium alloy practice—oxygen as the major impurity (in terms of influence on mechanical properties) and the others as major alloying additions. The composition and temperature ranges of investigation varied according to the system as shown in Table I. The principal means of investigation was light-microscopy. The basis of the ternary studies was the recently determined titanium-rich end of the Ti-A1 system.' MATERIALS, METHODS, AND PROCEDURES Ingots were prepared in 15 g size for all alloys except those of the Ti-Al-Mo and Ti-A1-V systems which were prepared in 20 g size. These alloys were prepared from high-purity, electrolytically refined titanium obtained from the Bureau of Mines, Boulder City Metallurgical Laboratory, Boulder City, Col., and Chicago Development Corp., Riverdale, Md., for the 15 g and 20 g ingots, respectively. The alloying additions were obtained from commercial sources, and were at least of 99.9 pct purity, except the V-15 wt pct A1 master alloy for vanadium additions. This alloy was of 98.2 pct purity; the major impurities were 0.37 wt pct Fe and 0.38 wt pct Si. The ingots were prepared by multiple melting in a nonconsum-able-electrode arc furnace. The ingots were covered with Markal coating "CR-T22" (Markal Co., Chicago) to protect them from scaling. Markal coating is applied as a slurry of solids in a volatile carrier liquid. The coated article is air dried. Upon heating to the hot working temperature the coating fuses to form a glassy, protective film. The ingots were heated to 1000°C and rolled to 0.16 in. thickness, reheating after each pass. The glassy film was removed by sand blasting. Ten mils were removed from all surfaces by grinding and/or pickling (3 pct HF, 30 pct HN03, balance water). Grinding was always followed by pickling to remove traces of the grindmg medium. Hydrogen removal was accomplished by vacuum annealing at 1000°C for 2 hr to a final pressure of about 0.02 µ Hg. This was followed by annealing in evacuated Vycor bulbs (800°C, 2 hr, ice brine quenched (IBQ)) in order to maximize ductility. The materials were then lightly pickled and cold rolled to 0.12 in. thickness or cracking, whichever occurred first. After rolling, 1/2 by 1/4 in. specimens were cut for the equilibration anneals given in Table 11 and carried out as previously described.1 Final polishing of the specimens for metallographic examination was done by electrolytic means. Specimens were first examined without etching under bright field and polarized light illumination, for this is the only means of detecting the "two-phase" phenomenon.1,2 The term "two-phase syndrome" refers to Ti-A1 al-loys which appear on the bases of their chemical, phys-ical, and mechanical properties, to be two-phase, but are actually single phase and inhomogeneous in composition. Since processing and heat treatment of the alloys of the first group were completed before the two-phase syndrome was discovered, a number of the specimens were found to exhibit this phenomenon—80 pct of those of the Ti-Al-Zr system, 5 pct of those of the Ti-Al-Sn system, 30 pct of those of the Ti-Al-Zr system. The affected specimens were homogenized by heating above the ß transus temperature and quenching. The heat treatment and working schedules to accomplish this are given in Table 111. After rolling, specimens were pickled (3 pctHF, 30 pct HNO3 in water) to remove 1 to 2 mils from the

Jan 1, 1970

By Sidney G. Parker, Jack E. Pinnell

Cubic ZnSe crystals have been grown with HCl, HBr, and I, as chemical transport reagents. The growth of large, well faceted crystals is in the order HCl < HBr < I, with some produced by I, transport being 1 cm on an edge. ZnSe:I crystals showed no strain in cross polarized light and were homogeneous as determined by electron microprobe. These ZnSe:I crystals had a mobility at 25°C of about 300 sq cm per v-sec and contained 103 dislocations per sq cm; further, these crystals were pure cubic and showed both photolumi-nescence and photo conductance. Doping was attempted during crystal growth. ZnS and Zn (S,Se) crystals were also grown by I, transport. ZnSe crystals have been grown by most of the common techniques.1"6 Of these, chemical vapor transport as developed by Kaldis2 showed promise of producing high perfection, cubic ZnSe. With chemical transport, crystals can be grown far below the transition temperature for conversion of cubic to hexagonal structure. A small temperature gradient between source and growth region tends to allow near equilibrium growth, which should lead to good crystalline perfection. Because it is necessary to form volatile compounds, halogens or their compounds are extensively used as transport agents. HCl, HBr, and I, were compared as transport agents for growth of ZnSe crystals. Doping during crystal growth was attempted. ZnS and ZnSxSe1-x crystals were also grown by chemical transport. Electrical and optical properties of the crystals were examined. EXPERIMENTAL Fig. 1 is a sketch of the growth apparatus, which was a modification of Kaldis&apos;. A quartz rod which butted against the seed crystal served as a heat sink to promote growth only on the seed. Initially, crystal growth was attempted with ZnSe prepared by wet chemical methods. Because such a material contained oxides and selenates, HC1 reacted with these oxygen compounds to form H2O and no ZnSe transport occurred. Further, this ZnSe contained about 10 ppm Cu plus other impurities. High purity ZnSe, containing small amounts or no oxygen compounds, was prepared by reaction of H2Se with zinc vapors at 600° to 800°C in an atmosphere of palladium diffused H2.7 The ZnSe thus produced was usually copper free and contained only 1 ppm by weight of magnesium as determined by emission spectrographic analysis. G.E.&apos;s electronic grade ZnS, which had about 10 ppm metallic impurities, was used without further treatment. ZnS-ZnSe charges were prepared by mixing the two compounds together, then sintering 24 hr at 1100°C in an H2S ambient. The gases, HBr and HC1, were commercial grade, of 99.9 pct purity, while the I2 was 99.999 pct pure. The single crystal seeds with (111) faces for growth were mechanically held in place by sealing the outer quartz tube to the growth tube. After the charge was introduced, the system was outgassed at l0-5 torr while heated to 500°C. The desired quantities of transport reagents were then sealed off in the system, which had been cooled to 25°C. The growth tubes were inserted into a furnace with the desired temperature and thermal gradient. The system was allowed to cool for 1 to 12 hr from growth temperatures of about 850" to 25°C. The tubes remained stationary during crystal growth. HCl CHEMICAL TRANSPORT GROWTH Preliminary runs with HC1 had a temperature gradient of 100° to 200°C and no seed or heat sink. Only small crystals were obtained in these experiments as

Jan 1, 1970