Search Documents

By Paul F. Fulton, Robert K. Estes

INTRODUCTION Relative permeabilities are factual data necessary to any prediction of reservoir production behavior. One important problem in determining relative permeabilities of porous media to gas is the effect of gas slippage on these determinations. Since certain aspects of the slippage phenomenon still remain unknown, this study is particularly concerned with that problem. The validity of the theory of gas slippage as it is applied to the flow of gas through porous media has been well established. 1,2,3 Therefore, in determining the permeabilities of porous media to gas by ordinary laboratory procedure, i.e., at atmospheric pressure, the slippage correction should be considered. Rose3 performed experiments on gas relative permeabilities which indicated that the effect of gas slippage on the measured effective gas permeabilities at various liquid saturations decreased with an increase in liquid saturation. Following Rose, it was substantiated experimentally' that the effective gas permeabilities at the various liquid saturations extrapolated to infinite mean pressure were the same as the non-wetting liquid permeabilities at the same saturations. This same paper also presented data which showed that the magnitude of the slippage between those values of gas effective permeability determined at atmospheric pressure and those found by extrapolation to infinite mean pressure decreased with an increase in liquid saturation. However, these experiments were not performed at liquid saturations above 30 per cent. Therefore, the purpose of this experimental work was to determine the effect of gas slippage on permeability measurements at liquid saturations in excesh of 30 per cent. APPARATUS Five core samples were used In this work: two synthetic Alundum samples (A-1, and A-2). a Nichols Buff sandstone sample (NB-13), and two samples from producing formations, a Soso sandstone (S-1), and a vugu-lar dolomitic limestone (R-7). The core samples ranged in permeability from 32 to 663 md. These cores were chosen because they represented a fairly wide range of permeabilities and probably a considerable difference in pore size and pore size distribution. Fig. 1 is a schematic diagram of the apparatus which consists of an air dehydration filter A, two Moore null-matic sub-pressure regulators B and C, the differential oil manometer D, the core holder E, the flowmeter F, the soap reservoir G, and a mercury manometer H measuring the downstream pressure. The interesting features of the apparatus are the two Moore vacuum-pressure regulators. The regulators permit the rapid establishment and easy control during flow at sub-atmospheric pressures of both the differential and downstream pressures, and prevent the surging action of the vacuum pump from disturbing the system during flow. Provided there are no leaks in the system, these regulators will maintain without measurable change selected downstream and differential pressure. Specifically, regulator B controls the downstream pressure and regulator C controls the differential pressure. In opera-

Jan 1, 1957

By J. J. Calaman, D. H. Fleming

DURING 1950 the jet-piercing process was used commercially in the piercing of primary blast-holes in magnetic taconite at the preliminary taconite plant of .the Erie Mining Co., Aurora, Minn. The Erie Mining Co. purchased a jet-piercing machine and associated equipment in 1949, and the machine has been in operation since its installation in the summer of that year. An overall view of the pit with the JPM-1 jet-piercing machine in operation is shown in Fig. 1. During three months of 1949 and continuously since February 1950, production piercing took place under all pit conditions. By the end of October 1950, a total of 15,000 linear ft of hole had been pierced in an open pit handling an average of 1200 to 1800 tons of crude a day in one 8-hr shift. While it is recognized that this output does not approach the millions of tons a year planned for the developing Minnesota taconite projects, the machine as a unit has been operating under conditions probably more adverse than those that eventually will be encountered in the large operations. This pilot operation has permitted evaluation of the piercing problem in the full-scale taconite plant. This paper describes jet-piercing process funda- mentals, important features of the latest jet-piercing burners and machine, actual piercing results obtained, and new developments that give promise of materially increasing overall process efficiency. To produce the blasthole, jet-piercing utilizes thermal energy, as contrasted with the application of mechanical energy in churn drills and jackham-mers. The heart of the process may be termed a tailored flame produced by a rocket-type burner, thermodynamically similar in every respect to that of the giant rockets being developed for military purposes. The heat release in the combustion chamber of the burner is about 50x10' Btu per cu ft per hr as compared with 5x10' for most modern steam generators.* Combustion of liquid petroleum fuels (kerosine, diesel oil, or No. 2 fuel oil) with gaseous oxygen in the burner chamber at pressures of 100 to 200 psi results in temperatures of about 4300°F. Expansion of the hot combustion gases through divergent nozzles produces high-temperature supersonic jets having measured velocities of about 6000 fps. Impinging the flame jets on rock causes a thin surface layer to expand and break away from the base as a result of the thermally induced stresses. This spalling action is aided further in chert and quartzite by the 0.82 pct volume change resulting from the 6 to p quartz inversion at 1066"F.t The dynamic action of the jets whisks the spalled rock

Jan 1, 1952

By T. J. Bosworth

The effect of hydrogen pretreatment of alumina, magnesia, and zirconia crucibles on reduced oxygen levels in iron charges has been studied. Hydrogen treatment of commercial high-purity magnesia crucibles was observed to produce as high as 70 pct reduction in oxygen content in iron melts. Hydrogen treatment of the commercial high-purity grade zirconia crucibles produced a 25 pct reduction in oxygen levels in iron melts. An average reduction of Knoop hardness of 47 pct was recorded on the iron charges melted in hydrogen-treated crucibles. On the basis of the experiments and the free-energy diagram, it appears that the major source of reducible oxygen to the iron charge is the suboxides and impurity oxides rather than the major oxide of the crucible. Suitable pretreatment of the crucibles to reduce and remove these oxides yields low oxygen levels in iron melted in the crucibles. DURING the last decade, attempts to produce more pure and uniform alloyed metals have brought about the development of many new melting techniques. Notable among these are vacuum-induction melting, inert and consumable-electrode melting, the cold-mold technique, and numerous techniques for removal of impurities by chemical reaction. However great the achievements in this field, metals must still be melted in contact with media of varying reactivity; i.e., gas, ceramic, and slag. Studies have been made to attain an understanding of the reactions that take place during melting, including slag-metal reactions and equilibria, equilibrium of hydrogen and water vapor, and carbon dioxide and carbon monoxide with oxygen in molten iron. These reactions have been treated quite thoroughly. There is one condition, however, that has been widely overlooked, and, to the author's knowledge, only cursive investigation has been made of it. This is the reaction between the ceramic crucible material and the iron charge. In recent years, Hadley and Bianchi' made a series of studies on hydrogen deoxidation of iron in magnesia crucibles. Bianchi2 studied crucible-FeO equilibria in the temperature range 1525°to 1650°C in high vacuum with, however, inconsistent results. Richardson and Jeffes3 in their series of articles on thermodynamic reactions in the making of iron and steel refer to Wentrup and Hieber's4 work on iron and aluminum deoxidation. Their pork included melting iron in alumina crucibles and measuring the aluminum and oxygen content in the iron. Because of the low values obtained, question has arisen of their analytical accuracy.3 Dastur and chipman5 obtained values on hydrogen-oxygen equilibrium in molten iron contained in alumina crucibles similar to those obtained in experiments in the present program. Hochmann6 studied removal of impurities in chromium irons in high vacuum. His results with respect to oxygen level in chromium-iron melted in magnesia crucibles are consistent with results we have obtained.

Jan 1, 1959

By A. Madrazo

The Standing-Katz method for predicting liquid densities of reservoir fluids has been tested using experimental data of 154 bottom-hole or recombined reservoir fluid samples. New pressure- and temperature-correction curves for the Standing-Katz type correlation are presented which improve the accuracy of prediction. INTRODUCTION The present study was undertaken to investigate the known methods of determining liquid densities and to select one of them which might yield a better correlation if additional data were employed. An appropriate correlation would incorporate the following characteristics: (1) ease of handling in the computations, (2) results within engineering accuracy and (3) data easily accessible. After careful investigation of the different methods, the Standing-Katz correlation1 appeared to have these characteristics. The Standing-Katz correlation for liquid densities of hydrocarbon systems is based upon limited data. The original work, which employs apparent densities for methane and ethane, was based on data of 15 saturated crude oils in equilibrium with natural gas. Therefore, a test of the correlation using additional experimental data would serve either to validate the Standing-Katz correlation or to form a basis for corrections if such were necessary. PROCEDURE AND GRAPHICAL SOLUTION The data of 154 bottom-hole or recombined reservoir fluid samples were employed to calculate the densities at 14.7 psia and 60°F by the method described in Table 1. Volume contributions for methane and ethane were assigned from the pseudo liquid density plot (Fig. I), but volume contributions for N2, CO2 and HzS were not considered. The densities computed at reference conditions of 14.7 psia and 60°F were then elevated to their respective temperatures and pressures by the use of the correction curves proposed by Standing.' The percentage differences between the experimental values and the calculated values were determined; these samples were grouped into temperature, pressure and density ranges to determine a possible trend. It appeared that, at temperatures above 160°F, the calculated density values were consistently larger than the experimental density values; however, no obvious trend was found for the density and pressure ranges. There is a relationship between the pressure-correction and temperature-correction curves. This relationship, embodied in the temperature-correction curve, can be expressed as follows. The experimental densities of 125 samples above their bubble points were known. From these isothermal data, it was possible to determine an experimental-density difference between two pressures; and (from Fig. 2*), a calculated density difference between the same two pressures was determined. The relative effect of temperature must be considered in the calculated-density values. The effect of temperature can be determined by entering Fig. 3* at the two densities in consideration and obtaining the change in density at constant temperature. This change, or delta density, must be added

Jan 1, 1947

By Robert U. King

The Climax Molybdenum Company's mine is situated on the Continental Divide at Fremont Pass in Lake County, Colorado. Elevations at the mine range from 11,000 it. to over 12,000 ft. The ore body is on the south flank of Bartlett Mountain, a prominent peak in the Ten Mile Range. A horizontal section of the mine, such as the Phillipson level (Fig. I), shows the outer ore zone as an annular ring varying in width from 300 to 800 ft., surrounding barren silicified rock. In vertical section the outer ore zone is dome shaped (Figs. 2 and 3), the apex of which is truncated at the surface by glaciation, exposing part of the ore body. The outer ore zone overlies the barren core and is itself overlain on the flanks of the dome with unmineralized rock. An ore zone of similar shape underlies the barren core of silicified rock, known as the Central Ore Zone (Figs. 2 and 3). Molybdenite is distributed uniformly through a zone of moderately silicified granite, schist and quartz monzonite (early) porphyry, around a highly silicified core. The molybdenite occurs in veinlets associated with fine granular quartz and pyrite, replacing altered and fractured granite, schist, and porphyry, and as coatings on numerous fractures cutting these rocks. Intense fracturing of all rocks is a characteristic feature of the Climax ore body. Most fractures are mineralized and no longer represent planes of weakness. Much fracturing is postmineral, however, and these fractures are generally filled with sericite or gouge, or remain as unmineralized joints separating otherwise massive rock into blocks of various size. Study and Mapping of Caving Characteristics Important differences in the behavior of caving of various blocks of ore at Climax have been recognized, involving arching of the rock over caved stopes, tendency of caved rocks to funnel, and size of caved rocks. Also, new problems have arisen associated with future mining on the Phillipson level, and may occur with proposed development of lower levels, such as excessive stress on mine pillars caused by large masses of overlying stable rock, and higher costs in maintenance of mine workings in soft, weak rock. To explain the differences and to provide solution for these problems, a study of geologic structure was undertaken early in 1944, to determine whether it would be possible to map cavability of rock from physical features exposed in mine workings and in diamond-drill cores. A comparison of known caved areas was made and rocks were classified structurally according to strength or degree of cavabil-ity. As nothing of this nature had been done before at Climax, the approach to the problem was rather indefinite. Several trials were made with negative results, but collectively indicated a suitable method. This was to examine all mine workings and diamond-drill cores, record-

Jan 1, 1946

By Don M. Jackson

The techniques for the growth and controlled, graded doping of silicon epitaxial overgrowth layers were established. Grading of- impurities such as arsenic or boron in arbitrarily chosen profiles oiler four orders of magnitude (from I X 10Lg to 1 X 10L5 cm) was accomplished. The graded structures were grown in a stepwise manner where in the profiles were approximated by growing many separate layers with small doping-level changes between layers. Masked-area growth of silicon through windows in a SiO2 masking film was acconiplished through the simultaneous injection of HCl gas 102th Sic14 in the epitaxial reactor. The HCl served to inhihit the growth of silicon on the Sz02 surface, and also to control the cross-sectional profile of the silicon mesas. silicon from the substrate was etched out through the windows, and then epitaxial material was used to fill the holes hack in to form planar diodes. Simullaneous HCl injection was adapted to control the cross-section profile of the hack-filled regions. Arsenic-huried regions beneath in te- In recent months, the epitaxial growth process in semiconductor materials technology has evolved into a complex system directed at both material improvement for better monolithic integrated-circuit characteristics and the development of new silicon structures for future integrated-circuit needs. The advent of high-temperature HC1 gas etching1 grated-circuit transistors reduced V(SAT) by slightly more than one third, bringing this parame-ter to that of an isolated component transistor. When arsenic was diffused into the starting sub-stvate, it was necessary to remove any excess arsenic in order to avoid excessive audodoping of the subsequent epitaxial layer. Oxide isolation of single-crystal regions in a substrate provided complete electrical isolation of integrated-circuit components, thereby eliminating parasitic capacitance which is inherent in standard integrated-circuit processing. The process involved the etching of deep mesas on silicon Wafers, the formation of an oxide over the mesa surface, and then the deposition of several mils of polycrystalline silicon over the oxide. The original substrate was lapped and polished allay until the mesas were left isolated in the polycrys-talline matrix. The Final components were fabri-cated in the single-crystal islands. Speed and power-handling capabilities of standard circuits were improved through the process. wherein work-damaged material is removed from the surface of the silicon wafer just prior to the silicon deposition step has made it possible to grow silicon films with structural quality that approaches that of the substrate. HBr used in the same volume ratio as HC1 etches silicon at the same rate and with the same results as HC1. Recent developments in epitaxial materials technology have occurred in the areas of precise doping control, buried prediffused regions between over-

Jan 1, 1965

By Frederick W. DeVries

Since we first agreed to present this talk we have learned that some of you may have been covering ground we intend to discuss: Bob Schechter, Daryl Tweeton, Don Seidel, Herb Burgman; however, the ideas were original when we began, "novel" as in the title of the talk, and whether our results are news or merely corroborative, we feel they point a direction that could be valuable to all. We worked with many of you in the past on using hydrogen peroxide in in-situ uranium leaching. Our talk today is not directly related to peroxide; it is, I hope, illustrative of Du Pont&apos;s interest in providing service to this industry in any way we can. The scouting work we are presenting was stimulated by field inputs: First, ammonium carbonate leaches cause restoration problems, primarily because ammonium ions exchange on clays with calcium. Second, sodium carbonate solutions, especially in South Texas deposits, can cause intolerable swelling of clays. From discussions with Dr. van Olphen, who wrote the book on clay chemistry, we inferred by comparison of the radii of the hydrated ions of the elements in these clay systems, that since potassium had about the same radius as ammonium, and sodium was much larger, potassium occupied a unique position to solve both problems. We have shown: FIGURE 1 Potassium bicarbonate systems leach uranium without loss of permeability found with sodium Potassium salts are very effective in restoring ammonia-leached sites Before reviewing the details of our work, which was performed by Hazen Research, Inc., I should like to stress its scouting nature. We are trying to assist the in-situ industry by pointing out new, potentially important directions. But, as with our previous work on sodium silicate to restore permeability, we feel the development phases can generally best be carried out in cooperative programs with companies directly involved with operations. DISCUSSION Test Parameters Now for the details: Our leaching tests were designed to note pressure-drop changes across the ore sample as the uranium was leached. Figure 2 shows the apparatus. The [ ] packed length was 20.5 inches (52 cm) with fifteen hundred grams of ore in the two-inch (5 cm)-diameter bed. Pressure drop was measured by manometer and feed rates were maintained constant with a tubing pump. The samples, from a South Texas leach site, were sealed in "Zip Loc" bags, frozen with "dry ice", crushed (still frozen) through six mesh, and blended before placement into the columns. The ores analyzed as shown here: FIGURE 3 Ore Analyses [Sample A Sample B U308 015% 0122% Mo 0004% 0086% Se0012% <0001% Fe3,078%076% Fee- 098% 044%]

Jan 1, 1979

By James E. Berryman

A method is presented for calculating the pressure depletion performance of a gas-condensate reservoir from the original reservoir fluid composition using the laboratory determined pressure-production history and retrograde liquid accumulation as guides. Equilibrium vaporization ratios for this calculation were modified from published data until the calculated dew point pressure and retrograde liquid accumulation agreed with the values observed in the laboratory. The calculated results are compared with the produced gas composition determined by low temperature analysis during constant volume laboratory experiments of pressure depletion behavior. This comparison shows that the calculation procedure is adequate for determination of gas phase composition. Data from field separation tests in low temperature separators are presented which verify the applicability of published equilibrium vaporization ratios for a wide range of separator conditions. INTRODUCTION A reliable prediction of the pressure depletion performance of a gas-condensate reservoir is necessary in determining reserves and evaluating field separation methods. The predicted performance is also used in planning future operations and studying the economics of projects for increasing liquid recovery. Because the flow of fluid in a volumetric gas-condensate reservoir is usually single phase flow, the pressure-depletion per-formake is primarily a function of the phase behavior of the reservoir fluid. The properties of a gas-condensate system of major importance are: (1) compressibility factor at reservoir temperature and pressure; (2) dew point pressure; (3) composition changes of the vapor phase with pressure depletion; (4) recovery of original in-place hydrocarbons at any pressure; and (5) retrograde condensate accumulation. These properties are most generally determined by a pressure depletion-type experiment on recombined separator gas and liquid samples in the laboratory. ldeally the pressure-depletion performance can be calculated from the composition of the original reservoir fluid if the reservoir temperature and initial pressure are known.1,2,3 It has been reported "... comparison of such computations with depletion-type ex-periments on recombined samples in the laboratory have yielded results that appeared to be entirely adequate.". The success of such calculations is determined by the equilibrium vaporization ratios chosen, especially those for the higher boiling point hydrocarbons. It is the purpose of this paper to present a method for computing the change in composition of the vapor phase during pressure depletion by production using laboratory determined properties of the system to guide the calculation and to illustrate the use of the method with data from the Cockfield "D" sand of Washington field, St. Landry Parish, La. Results of field tests and laboratory analysis are included. As a result of this reservoir fluid study, a cycling program has been evaluated, the fidd has been unitized, and the cycling started in July, 1956.

Jan 1, 1958

By C. Richard Honeycutt, Frederick C. Langenberg, Guenter Pestel

Otto Schaaber (Institut für Harterei-Technik, Bremen-Schönebeck, Germany)— Langenberg, Pestel, and Honeycutt gave an interesting example of the grain refining effect nonstationary magnetic fields may execute on a solidifying metal. Probably some additional comments, based on more than a decade of experience with this method of influencing crystallization, may be useful. They refer to an attempt to explain the mechanism of grain refinement by such fields, and to recent European developments which have not been mentioned in the paper. I. During studies of the temperature distribution in a metal body near the phase boundary solid/liquid, an anomaly was observed under certain special conditions: a) direction of heat transfer as horizontal as possible, b) steady state (equilibrium, i.e,, solidification resp. melting rate exactly zero). In the liquid phase, immediately adjacent to the phase boundary, the temperature was found to be constant over an appreciable distance in spite of a high value of heat transfer (40.000 to 70.000 keal/ m2h).3 Convection, which might explain this phenomenon, could not be observed. Therefore another explanation had to be sought. The assumption that a metallic melt, especially at temperatures near the point of solidification, contains some sort of atomic arrangement with a higher degree of order than the surrounding liquid, now is generally accepted. Considering the differences in energy between such an arrangement and its environs, a transport of heat even in absence of any temperature gradient is conceivable by continued formation and redissolution of regions with a higher degree of order, i.e., with lower energy level.3 At this stage, it was not necessary to postulate any special condition as to the form or size of these regions or the distance between arrangements to be newly formed and those to be redissolved. However, a simple consideration shows that an energy transfer from one region to another will only be possible without loss of energy, if the distance between will be equal to the lattice parameters, and if, secondly, crystallographic axis or planes will be parallel.4 By the way, this assumption might give a reasonable explanation of the well known orientation effect of the heat flow during solidification. Any measures to prevent columnar crystallization should act upon this ordering mechanism: a) the regions with a lower energy (higher order) should not be allowed to arrange themselves parallel to the direction of heat flow, and their growth should be disturbed; b) all conditions leading to an appreciable heat flow of uniform direction should be avoided or removed. Condition a) may be satisfied by a physical force preferably under 90 deg to the main axis of the columnar crystals (i.e., parallel to the solidification front) acting on the ordered regions; condition b) by equalizing any differences in

Jan 1, 1962

By J. L. Shafer, Christopher L. Caenepeel, Martha L. White

Often an in situ leach is the only practical economic method for copper recovery from small low grade oxide deposits. The decision to develop a copper property by an in situ blast and leach is strongly dependent on ore grade, tonnage, hydrology, and the copper extraction and acid consumption rates. The inherent leachability of the ore will in part determine the desired amount of fracturing of the ore deposit by the blast in order to obtain a copper extraction rate that is economical. For the last several years Occidental Research Corp. (ORC), has undertaken a modest effort to address the question of how to best identify and determine the information necessary to predict and control the operation of an in situ leach for the economic recovery of copper. Modelling of the Leaching Process During the past 10 years the activity in the mathematical modelling of the leaching of copper sulfides in copper dumps and heaps has increased dramatically. The modelling of copper oxide leaching has not received as much attention. The acid leaching of non-sulfide copper minerals while chemically less complex, compared to sulfides, does generate a vertical acid concentration gradient in the ore heap being leached due to the acid-base nature of the reaction. This is generally not observed in sulfide deposits that are biologically active, due to the buffering action of opposing reactions involving the generation of sulfuric acid from sulfide minerals and acid consuming host rock. Thus, the objective of ORC &apos;s copper oxide modelling efforts is to determine the leaching parameters which will account for this vertical acid concentration gradient. Knowledge of this gradient will result in the correct choice of the feed acid concentration to the top of the ore dump or heap, such that the effluent will have the desired pH.

Jan 1, 1980

By William F. Harris, Joseph Easha

FOR many years basic control of refinery operations depended on visual observation of small chill specimens poured at various intervals during processing. The oseto of these samples was related to the physical and chemical properties of the metal. Since the =setn is dependent on many factors other than oxygen content, this method, while giving a general indication of the condition of the copper, does not accurately measure the oxygen content. For the last 3 years a modified vacuum fusion procedure which enables the operator to determine the oxygen content of the copper within 1 5 min of sampling has been in use at the Westinghouse Copper Mill. For use with this apparatus a sampling technique has been developed which gives oxygen values representative of the oxygen content of the wire bar. The sampling technique is based on a statistical study, which compared the oxygen content of the laboratory sample of copper poured at the same time a wire bar was being poured, with the oxygen content of the wire bar. The apparatus used for the determination of oxygen in copper is shown in Fig. 1 and is essentially the same as previously described but with one important modification. A very porous fritted glass disc has been inserted in the tubing between the manom- eter and 40/50 ground glass joint. The fritted disc retains the copper vapor and copper particles in the furnace section and prevents contamination of the mercury in the manometer. Without the disc the manometer became difficult to read after a few weeks of operation. In earlier work1 it had been established that the simplified vacuum fusion apparatus used at the Copper Mill gave essentially the same results as a con-vential vacuum fusion apparatus. However, for this study it was necessary to determine the difference, if any, between the oxygen content of the wire bar and the oxygen content of the small chill sample used for the oxygen analysis. This correlation was established by taking a chill sample at the same time wire bars were being poured. The wire bar being poured at the time the chill sample was taken was marked and removed for further analysis. The copper is sampled at various times during refining and cast into laboratory size samples with the mold shown in Fig. 2. The mold is made of cold rolled steel and is 2 in. high and 2 1/2 in. in diam. The large upper portion of the cast sample is used for measurement of the conductivity of the copper, The lower portion which is a rod about 1/4 in. diam by 3/4 in. long is used for determination of the oxygen content. This portion of the sample weighs about 5 g which is approximately the size sample used for the analysis. The only preparation neces-

Jan 1, 1962

By F. H. Turan, F. W. Jessen

The gel strength and viscosity of two different suspensions of fractionated montmorillonite clay were measured by using a Stormer viscosimeter and Farm V-G meter. The amount of sodium poly-phosphate (sodium bexametaphosphate, sodium tetraphosphate and sodium acid pyrophosphate) adsorbed by the clay particles was determined. A relationship seems to exist between the amount of polyphosphate adsorbed and the nature of the surface, edge or plate, assumed to be the principal sites for selective adsorption. Reduction in viscosity and gel strength was found to be directly related to the adsorption. Both chemical bonding and physical adsorption seem involved in defloccula-tion Some indication of the axial ratios of particles of .l- to .04-micron average size is possible though study of the adsorption mechanism. INTRODUCTION AND PURPOSE A knowledge of surface areas of clay particles in a suspension and a precise determination of phosphate adsorption should provide a basis for a better understanding of reduction in viscosity and gel strength caused by molecularly dehydrated phosphates. The purpose of this investigation was to study the adsorption of sodium polyphosphates on suspensions of fractionated sodium montmorillonite. Although there is considerable uncertainty regarding details of the structure of montmorillonite, a generally accepted one is that suggested by Hofmann, Endell and wi1m.l The structure shown in Fig. 1 is an idealized one, and Marshall2 has postulated that it is possible for several isomorphous replacements to occur. Thus, aluminum may replace silicon, in which case an exchangeable cation would go along with the aluminum to neutralize what would otherwise be a net negative charge on the structure. There is disagreement among various investigators as to the particle size and shape of montmorillonite clays. Marshall2 reported the following results for the mean lateral dimensions of a Putnam clay (montmorillonite)— 3,730 A° for particles having average diameters ranging from 500 to 1,000 A, and 750 A° for those with an average diameter less than 200 A. The latter particles were estimated at 50A°in thickness, which would correspond to a stack of five unit cell layers. On the other hand, Shaw3 has interpreted micrographs as indicating that particles of montmorillonite ire readilv broken down to the individual cell layers by dispersion in water. Brindley4 and Merings indicate the ultimate particles to be of the order of 300 A° in mean lateral dimension. Van Olphen6 suggested the thickness of particles at four to five unit cell layers. It was suggested also that this number tends to become smaller with increasing dilution. Recently, Kahn and Lewis7 determined the size of sodium montmorillonite particles in aqueous suspension from electro-optical bi-refringence decay curves. The

By W. Rosotoker

Using an expression for the free energy of a homogeneous phase as a function of composition, a relationship is derived which interrelates the phase boundaries extending from the allotropic transformation of the solvent metal. Comparisons between observed and calculated phase boundaries in the systems Fe-Ni, Fe-Mn, Fe-W, Ti-Mo, and Ti-Cb are presented. IT is the purpose of this paper to illustrate how the general free energy equations for two phases in equilibrium may be used to derive an expression which interrelates the phase boundaries extending from the allotropic transformation of the solvent metal. The free energy per gram atom of a disordered solid solution may, for many purposes, be represented by the equation:&apos; F = ½NZ [C-V,, + (1-C) VbB + 2C (l-C)V] + K(T) +RT[C-lnC+ (l-C)ln(l-C) ] [1] where N is Avogadro&apos;s number; Z, the coordination number; C, the concentration of the solute element in atomic percent; the subscripts refer to concentrations at phase mixture boundaries; VAA, VBB, and V,, are the bond energies between like and unlike adjacent atoms, respectively, at the interatomic spacing characteristic of the phase. The bond energies are usually assumed to be independent of small changes in the lattice parameter occasioned by solute additions and variations in temperature; V = VAB ---------------—— ; K(T) is the sum of the heat con- tent and heat entropy; R, the molar gas constant; and T, the temperature in degrees Kelvin. The free energy of a homogeneous phase is there- fore the sum of an internal energy, a specific heat, and a configurational entropy term, respectively. The compositions of two phases in equilibrium at a given temperature are governed by the minimum total free energy principle. Graphically, this is represented by the points of tangency of the tangent common to the free energy vs. concentration curves of the two phases. Analytically, this may be expressed as: ( df) = (df) [2] dc dc Expanding both sides using eq 1, the following equation is obtained after convenient readjustment of the terms: RT In[(ca)(1-c)]-½N (Vaa-Vbb)(Za-Zb) +NV [Za(l-2Ca)-Z,(l-2C,)] [3] The following assumptions have been made at this point: 1—The specific heats of the two phases are independent of composition variations within the range under consideration. Accordingly, the K(T) terms disappear on differentiation. 2— (Vaa)o = (VAA); (VBB). = (VBB); Va = V, Theyjustification for these assumptions can lie only in the successful application of the resultant equation. It may be noted that Zener2 has used assumption 1 in the calculation of the boundaries limiting the (a+j3) phase mixture in the Cu-Zn system.

Jan 1, 1952

By E. O. Chartkoff

IN 1926 one of the authors published researches on the determination and description of the iron-tungsten and iron-molybdenum systems,1 including the equilibrium diagrams. In 1929, further work was carried on, including the examination by X-rays, which is recorded here. Measurements were made of changes in lattice parameters in the solid solutions. Precipitation from the solid solution and the accompanying changes in hardness were studied as well as the formation of the intermetallic compound phases upon sintering a mixture of metal powders.

Jan 1, 1930

By A. E. Austin, J. R. Doig

Ti-Cr alloys age harden after B-quenching by formation of an W-phase. The structure and orientation of this transition phase have been determined. The hardness ap-pears to be caused by strain in the B-matrix produced by concurrent enrichment of alloy content in the W-phase. EARLY studies of age hardening in B-stabilized titanium alloys revealed the formation of a transition phase named o&apos; This phase was detected by X-ray diffraction in binary alloys of Ti-Fe, Ti-Cr,

Jan 1, 1958

By W. C. Winegard, C. Feng, C. Elbaum

SEVERAL investigations have been made concerning the effect of oxygen on the mechanical properties of titanium 1-6= In particular, the yield strength has received considerable attention. Finlay and snyder2 report a 0.2 pet strain offset yield strength if 49 kg per sq mm in titanium containing 0.1 pct 0 and 61 kg per sq mm in titanium with 0.2 Pct 0. These results are in good agreement with those of Jaffee, Odgen, and Maykuth3 who report values of yield strength

Jan 1, 1960

By H. A. Guess

For a number of years I have used for the commercial wet assay of lead generally the ammonium molydate, and occa-sionally the ferrocyanide method. These well-known methods need no detailed description here. In the ore-selling and ore-buying establiahments of the West, 90 per cent. of all wet lead-assays are made by one or the other, and at least nine-tenths of this proportion by the molybdate method. A procedure so well-established must have merit; and, in

Jan 1, 1905

By Arthur H. Leigh

Anode mud, the residual material collected from the bottom of the electrolytic cells during the refining of copper is leached, roasted, fire-refined and cast into Dore1 metal anodes. Dore1 metal is a gold-silver-copper alloy containing 80 percent silver. The metal is processed electrolytically using the Moebius system to refine silver and separate gold, platinum and palladium. The Moebius cell cathodes receive a deposit of silver crystals which are melted and cast into 1000 ounce silver bars with 999 Fine minimum purity. Gold mud is collected in fabric bags and cast into gold anodes for further refining in the Wohlwill cells. Wohlwill cells are unique in that gold, the noble metal, can be put into solution electrolytically without the use of aqua regia. Gold is collected on high purity gold foil cathodes and cast into 400 ounce bull ion with 999.7 Fine minimum purity. Platinum and palladium remain in the electrolyte progressively increasing in concentration and are finally separated and purified by precipitation.

Jan 1, 1973

By M. L. Samuels

In a recent paper the authors1 discussed the reactions to tempering of hypereutectoid steels quenched from 1000&apos; C., as revealed by studies on changes in hardness, electrical resistivity, coercive force and metallo-graphic charaeteristics. The data, which related specifically to tempering temperatures of 550°, 650" and 710" C., for varying periods up to 125 hr., permitted the following important conclusions: 1. The rate of softening of the steels at the temperatures examined differed markedly although the steels were of "similar" general chemical composition. 2. The temperature of maximum softening spread over a range from about 650" C, to the eutectoid inversion. 3. The divergence in behavior was ascribed, at least in part, to a profound difference in tendency to graphitization on annealing at sub-eutectoid temperatures. 4. The mode of spheroidization of the cementite, as revealed by metallographic studies, also varied considerably in the different steels. The purpose of the present investigation is to pursue further the study of the difference in behavior of the steels on tempering over a wider range of temperature. To this end the following features have received particular attention: 1. Comparison of temperatures of maximum softening of the various steels when the quenched samples were tempered for 5 hi. and for 75 hr. followed by furnace cooling and by quenching in water. 2. Deterrnirlation of the effect of quenching temperature, prior to tempering, on the rate of softening. Quenching temperatures of 1000" and 850" C. were used in the investigations. 3. Examination of the microstructures obtained with the various heat-treatments employed.

Jan 1, 1938