Search Documents

By O. J. Kensok

THE literature contains three previous studies of the chemical activities of Cd-Mg alloys: Trumbore, Wallace, and craigl obtained chemical activities of magnesium at 543" by performing electromotive-force measurements; Borg and irchenall calculated activities at 590°K based on vapor-pressure measurements of cadmium over Mg-Cd alloys by the Knud-sen effusion method; and Terpilouski and arcka measured the chemical activities of magnesium in the liquid state by means of electromotive-force measurements. In this study the vapor pressure of cadmium was determined over nine solid Cd-Mg alloys in the temperature range 571" to 697°K by the Knudsen effusion method. This study was prompted by the lack of precision in the data reported by Borg and Birchenall. Knudsen cells used during this study were fabricated from 0.020-in.-thick tantalum tubing. The tops and bottoms of the cells were cut from 0.010-in.-thick tantalum sheet, press-fitted, and welded in place. The orifice was drilled in the cell top and subsequently reamed to a knife-edge thickness. The diameter of the orifice was measured with a traveling microscope capable of reading 0.0001 cm. The sample was heated by means of a resistance

Jan 1, 1967

By Charles Catlett

Some years ago the writer was struck by what might be called the remarkable vitality of the Virginia furnaces during the panic of 1893; and attention was called to the fact in the American Manufacturer of February 8,1895. From the second half of 1892, which was a period of maximum output, to the second half of 1893, when the full effects of the depression had been reached, the output of pig-iron had fallen off in Illinois 85; in New York, 66; in Ohio, 51; in Tennessee, 44; in Pennsylvania, 28; and in Virginia only 15 per cent. It seemed a reasonable inference that the State which had thus shown its marked ability to meet hard times could make and market its product with a larger margin of profit than any of the other States. This was true at that time, and to a certain extent the reasoning still holds good; but my mistake was in not fully realizing the marked effect of the Mesabi development, combined with reduced economies in transportation, and the consequent advantage to those furnaces which were so situated as to utilize these new commercial factors. The effect of these factors is seen in comparing the second half of 1894 with the second half of 1892. New York had dropped off 44, Alabama 23, Tennessee 21, Illinois 19, and Virginia 16 per cent., while Pennsylvania had increased 5 and Ohio 10 per cent. While there is no question of the great economy which has been made possible for certain interests which are peculiarly situated with reference to the ores of the Northwest, it is yet too early to say what furnaces not so fortunate will have to pay for their raw material. Already an increase of twenty cents per ton of ore has been announced, based upon increased cost of production.

Jan 1, 1900

By Franklin H. Allison

The influence of cobalt and nickel on the properties of steel might be readily expected to be very similar. The two elements occupy close and somewhat unusual positions in the periodic table, their chemical behavior and compounds are so completely analogous and their various physical properties, including the ferro-magnetic characteristic, show such 3 remarkable correspondence, that there is no doubt of a strong resemblance existing between these two metals. However, the variety of properties that are obtained from steel is due largely to the fact that the element iron possesses allotropic forms. Alloying elements that affect these allot ropic forms, or alter the nature of the allotropic changes, exert a profound influence on the resulting steel. In the case of nickel and cobalt, although these elements are very similar chemically and physically, it is found that they differ distinctly in their individual effects on the critical points of iron. Both nickel and cobalt form a series of homogeneous solid solutions with iron at temperatures above 1500" F. The difference in their behavior does not occur until changes begin to take place in the solid state below this temperature. An inspection of the respective thermal equilibrium diagrams at the lower temperatures makes the opposite effects of nickel and cobalt clearly evident. Effect of Nickel and Cobalt in Binary Alloys with Iron The binary diagram of iron-nickel has been investigated by a number of workers. The lower temperature portion in Fig. 1 is reconstructed from the data of D. and H, Hanson.1 The diagram of iron-cobalt, shown in Fig. 2, is taken from the work of Ruer and Kaneko.2 Masumoto3 has recently discovered a lower critical point in cobalt and this has been added to the diagram. In both diagrams the space lattice structures as determined by Andrews4 have been included. It is interesting to note

Jan 1, 1927

By Eugene A. Stephenson

Critical analyses of the work expended in producing oil by the utilization of gas energy have appeared in the publications of Shaw,' Pierce and LewisI2 and Herold,3 authors who have ably discussed the factors which must be taken into consideration in comparing energy consumed per barrel in various wells which are flowed by means of gas-lift. However, two distinct phases of oil production are concerned with the ratio of gas energy consumed to oil produced. One of these phases is the gas-lift, which utilizes the differential gas pressures for the purpose of flowing oil, whether these pressures be natural reservoir pressures or be induced by artificial compression of gas or air. The other phase has to do with prorating oil production in pools which are operated either as units, or are subject to such restrictions as those imposed at Oklahoma City by the Corporation Commission, or by similar controlling groups in other fields. An abundance of literature is available relative to the problems of flowing wells by gas-lift, but the first suggestion that the energy of the gas within the oil and gas pool might serve as a basis for proration, appeared in the timely article by Mc Williams.4 Much of the dissatisfaction with proration in certain fields arises because some operators feel that besides the hazard to the wells which accompanies the test, the method of allocating production on the basis of the " potential" gage is inequitable and gives some operators a distinct advantage over others.5 The most severe penalty may be exacted from the most progressive operators or those who attempt to produce their oil with a minimum quantity of reservoir gas. If no difficulties ever developed in drilling, shutting off water, or in well completion, it might

Jan 1, 1931

By H. E. Cline

A criterion for stability of a lamellar structure in two-phase alloys ulas derived froflr perturbation analysis of the steady-state solutions for eutectic growth. Both the mass and thermal diffusion were considered with boundary conditions for coupled lamellar growth. The concept of an effective liquidus slope was introduced. Excellent agreement was found with the experiments of Mollard and Flemings and the theory predicted a range of compositions on one side of the eulectic composition in which stable growth may occur with zero temperature gradient. The lamellar structure was found to be more stable than predicted by simple constitutional supercooling. The effect of impurity additions was also considered. DIRECTIONALLY solidified eutectic alloys may have a structure consisting of parallel plates or rods. It is important to know the range of composition and growth conditions that produce this ideal composite structure. Breakdown of the planar solid-liquid interface during growth may lead to a dendritic or cellular structure as in single-phase alloys. In the case of single-phase alloys, the concept of constitutional supercooling1 may explain breakdown, but in two-phase alloys the concept is no longer valid because the melting point is not given by the liquidus of one phase. Both phases must be considered in the mass and thermal diffusion problem. In the following theory a boundary condition at the solid-liquid interface was determined by using the steady-state equations of Jackson and ~unt' to relate the average temperature and composition of the liquid at the interface. Then a sinusoidal perturbation in the shape of the interface was introduced to test for stability as in the analysis of Mullins and ~ekerka.~ The wavelength of the important perturbation was assumed to be much larger than the lamellar spacing, h, and the perturbation was assumed not to change the lamellar spacing, A. Both the mass and thermal diffusion equation were used with averaged quantities at the boundary to determine whether the perturbation grows or shrinks in time. A stability criterion was determined by considering the case in which the perturbation remains stationary. An example of Pb-Sn alloys was used to illustrate the validity of this theory. I) THEORY A) Temperature at the Interface. The temperature of the interface in coupled two-phase growth is close to the eutectic temperature TE even for alloys off eutectic composition. It is assumed that the interface is in local equilibrium and one expects the temperature at the intersection of the liquid phase and the solid phases a and 0 to be near the eutectic temperature. The interface is undercooled because of curvature and the deviation of the composition in the liquid from the eutectic composition. The average interface temperature Ti for steady-state growth of a lamellar eutectic with a plane interface was determined by Jackson and Hunt' as given in their Eq. [17c]. Instead of using the ratio of the lamellar widths hp/h, as a parameter, the volume fraction of the 0 phase, +, will be used as it simplifies the algebra. The average interface temperature using this notation becomes: The average temperature of the interface depends on the volume fraction of the 0 phase, +, which may be related to the composition of the solid or the bulk composition of the liquid Co by: where C, and Cp are the average compositions of the solid phases. In steady-state growth, the composition of the solid is equal to the composition in the liquid far from the interface. The variation of the average interface temperature with composition is illustrated in Fig. 1 for the case of Pb-Sn alloys with a 10"4 cm lamellar spacing as calculated from Eqs. [I] and [2]. The interface temperature goes through a maximum at a composition near but not exactly at the eutectic composition. There is no reason why the composition corresponding to the maximum temperature should be equal to the eutectic

Jan 1, 1969

By J. M. Markowitz

The movement of hydrogen in two-phase Zircaloy-2 under the influence of a thermal gradient was studied in specimens of cylindrical geometry. A gross displacement of hydrogen toward the cooler regions of the specimen was observed with consequent copious precipitation of 6-ztrconium (ZrH) there. The kinetics of the diffusion are analyzed and discussed. X HE temperature-gradient redistribution of hydrogen in a-Zircaloy-2 has been treated both theoretically and experimentally Hydrogen moves toward the cold side of the temperature gradient until a steady state has been established; tendency for further hydrogen movement because of temperature differences is nullified by the tendency to move in the reverse direction because of the concentration gradient. The steady state condition is described by the equation in which iV is the concentration of hydrogen at a point in the specimen corresponding to absolute temperature T, R is the gas constant,k is a constant of integration, and Q is a parameter called the heat of transport, characteristic Of the particular system. The value of Q has been determined for hydrogen in Zircaloy-2 by several investigators, using Eq. [11. There is considerable variation in the results, the cause of which has not been resolved; reported values lie in the range 3 to 6 kcal per mole. The physical situation for two-phase thermal migration is much more complex. The -phase boundary for the solubility of hydrogen in Zircaloy-2 ranges from a concentration of 25 ppm at 200°C to a maximum of about 600 ppm at 550°C.4a Thus, if the concentration of hydrogen in Zircaloy-2 is sufficiently great (>600 ppm), the specimen will be entirely two-phase, consisting of a matrix of a-Zircaloy-2 surrounding particles of zirconium hydride. At time zero, with a temperature gradient imposed, the relative amounts of hydride and a-phase in each infinite-simally thin isothermal section of the specimen can be determined from the phase diagram by the lever rule. Moreover, the concentration of hydrogen in the matrix phase varies from point to point, following the a solubility line. Over most of this temperature range (<450°C) 6 phase, Fig. 3, has a constant concentration.5 The diffusion rate toward the cold side should be governed by 1) the slope of the a solubility line and 2) the temperature gradient, The extra complication of two-phase thermal diffusion lies in the fact that migration of hydrogen would leave the a-phase concentration gradient unaffected, since it is fixed at any temperature only by the solubility; gross concentration changes would reflect only the relative amounts of matrix and hydride, which could vary continuously at every point. Migration of hydrogen out of a region would lead to dissolution of hydride, and

Jan 1, 1962

By H. C. Chang, N. J. Grant

Creep of very coarse grained high purity aluminum was studied at 400°, 700°, and 1100°F at initial stresses of 50 to 1200 psi. Local strain measurements were made across the grain boundaries and in different regions of various grains during creep, thereby permitting the drawing of component creep curves. The relative amounts of elongation as measured across a grain boundary and in the grains adjacent to the boundary depend on the temperature of testing. The significance of creep curve equations and activation energies is discussed. THIS paper presents some of the results of a research program devoted to the study of the mechanism of creep in high purity aluminum. Previous publications have dealt with the cyclic processes of alternating grain boundary sliding and migration, and the deformation in the grains caused by these processes;&apos; the direction and the driving force of grain boundary sliding and migration;&apos; the deformation in the grains and the restricting effects of the grain boundaries on this deformation." These previous papers were based mainly on either microscopic observations or X-ray data, or both. Sometimes creep curves across two closely spaced reference marks (about 0.6 to 0.7 mm apart) were also presented with a view to correlating the elongation values with the optical observations in general, and with certain deformation processes in particular. These curves shall henceforth be referred to as component creep curves. No attempts were made, however, to compare either the component creep curves which were obtained in different regions of a specimen, or those obtained from different specimens subjected to different creep test conditions. It is the purpose of this paper to present these component creep curves. Among the factors influencing the behaviors of these curves, those studied were stress, temperature, and grain arrangements in the specimens. It is proposed to show how greatly the deformation can vary from grain to grain and within an individual grain in a coarse grained specimen. The experimental technique and procedure have been presented.&apos; It remains necessary to emphasize that the reference marks were produced by pressing a thin sewing needle into the surface of the specimen before the final annealing at 900°F for 24 hr and at 1150°F for 12 hr. The cold work around the needle indentations was therefore removed. The depth of these holes after electropolishing the annealed specimens was about 0.01 mm. This depth and area were negligible in comparison with the thickness of the specimens, 2.3 mm, and hence would not affect the creep behavior. Results Fig. 1 shows a development diagram of specimen P-8. The dots on the surface locate the needle point reference marks used to obtain the component creep curves. A curve obtained between two dots across a grain boundary measures not only the boundary deformation but also the deformation associated with boundary sliding occurring in the grains in the region between these indents. The original distance between two reference marks was about 0.6 to 0.7 mm. The maximum error of measurement was 0.01 mm, or in terms of percentage elongation, of the order of & 1.5 pct. Whereas the component creep curves shown in the figures to follow were drawn as a gross average of the points, in view of the fineness of some of the steps of grain boundary sliding and migration, as shown in the previous publications,¹,2 it appears logical to expect that some of the finer cycles of movement have not been delineated for the strain sensitivity of the measuring system. It seems justifiable to say that the curves are not as smooth as shown. 700°F Tests: Fig. 2 shows component creep curves across four of the grain boundaries in specimen P-8, tested at 700°F and 85 psi. These curves clearly show alternate cycles of increasing and decreasing

Jan 1, 1954

By N. S. Stoloff, K. R. Jordan

The temperatwe and grain size dependence of the mechanical avoperties of ordered and disordered Fe-49 pct Co-2 Pct V were investigated. The yield and flow stresses obeyed the Hall-Petch relationship u = ai + kd-&apos;I2. Ohdering reduced the intercept stress cjj and raised the Petch slope, k, at all temperatures. Ordering also increased the temperatwe dependence of k. The ductile to brittle transition temperature increased with order and grair~ size. Cleavage fracture was nucleation limited and the fracture stress did not zlary linearly with d-&apos;". A quantitative test of the Cottrell-Petch fracture theory (and recent modifications which consider the influence of slip mode), demonstvated that this theory is not applicable to FeCo-V. COTTRELL&apos; and etch&apos; independently suggested that a criterion for cleavage failure at the yield point, a,, based on dislocation pileups at a grain boundary or other obstacle to dislocat.ion motion, is: aYYkd&apos;I2 1 opy [ll or, equivalently, aikz,d112 +k:)bpy [2] where a, and ky are the Hall-Petch intercept and slope, respectively, 2d is the grain diameter, P is a geometric factor dependent on the macroscopic ratio between shear and tensile stress, p is the shear modulus, and y is the true elastic surface energy. When the product of quantities on the left side of the equation is equal to or exceeds that on the right, cracks should be able to nucleate and propagate at the yield stress, as shown schematically in Fig. 1. Therefore a high intercept stress, high Petch slope, or coarse grain size favors brittleness. petch3 associated the existence of a ductile to brittle transition in ferrous alloys with the temperature dependence of ai. One of the earliest modifications of the Cottrell-Petch theory was presented by ~rmstrong,~ who derived an expression for transition temperature in terms of several measurable flow and fracture parameters. The latter paper was able to rationalize situations in which the transition temperature increases with decl-easing grain size, as in the case of molybdenum,&apos; and also suggested that Ppy should be a function of grain size as well as temperature. More recently Johnston et a1.6 and Smith and worthington7 have suggested that the temperature or composition dependence ol&apos; ky must also be taken into account if there is any cha.nge in deformation mode, as from wavy to planar slip, or wavy slip to twinning, with change in temperature or solute content. Armstrong %as suggested that for hcp metals changes in o;k,dw> o;k,d1/2< / is / ^^^^ / / y_______________________________________ d-"2 Fig. l—Schematic representation of grain size dependence of yield stress, cry, and fracture stress, CTF. Intersection defined by Cottrell-Petch equation. slip mode should be incorporated in the theory through changes in the critical resolved shear stress for the slip system which controls ky. The purpose of the present investigation was to critically test the modified677 Cottrell-Petch theory of fracture in the superlattice alloy Fe-49 pct Co-2 pct V, by studying the grain size dependence of the yield and fracture stresses over a range of temperatures, in conjunction with an investigation of slip mode and fracture behavior. Previous work has shown that long range order results in a sharp decrease in flow stress, a small increase in work hardening rate and a drastic upward shift in the ductile-brittle transition temperature of F~CO-V.~&apos;~ The only comprehensive study of slip character in this alloy has been reported in a preliminary account of the present investigation.10 EXPERIMENTAL PROCEDURE The experimental work was carried out on material produced from a 10 lb vacuum melted ingot, of composition 49.32 wt pct Co, 2.09 wt pct V, balance Fe. 30-mil thick sheet samples with a 1; in. gage section were machined from cold rolled stock. The degree of cold work ranged from 85 pct for the finest grained samples to 5 pct for the coarsest grain size. Details of ingot fabrication are reported elsewhere." Equi-axed grain sizes in the range 12.7 to 75.4 p were obtained by annealing for varying times at 850°C. (Re-crystallization annealing time, rather than temperature , was varied to control grain size to insure that samples of all grain sizes contained equivalent quenched-in vacancy and interstitial concentrations.) Grain sizes were measured by the line intercept method on several specimens of each grain size. Following recrystallization, all samples were disordered by quenching into iced brine.

Jan 1, 1970

By P. K. Koh, H. A. Lewis, H. F. Graff

New data on the distribution of silicon between slag and carbon-saturated iron at 1600Oand 1700OC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1&apos;700°C for slags containing up to 20 pct A12O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A12O3-SiO, slags over a range from zero pct Al2O3 to saturation with Al2O3, or CaO.2Al2O3. The upper limit of SiO2 is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/Al203 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al,O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al0 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al2O3 and of Al20,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO2 (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2. The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By R. P. Rothwell

THE first difficulty mentioned is that in some instances two or more beds of coal separated by sandstone or slate rocks of considerable thickness in one part of a basin, are found running together in another part. Of course, we may happen to strike first the part of the basin where there is but a single seam, and in this case the bed would appear 60 divide into two or more branches within a short, distance. Such cases are not rare in the anthracite coal-fields. I would suggest as an explanation of this phenomenon the gradual sinking of the peat-marsh-the embryo coal-bed-on one side, and the moving forward of the marsh, so that on one part of the bed the formation of peat would still be progressing, while another part, being under water, would be covered with mud and sand. Thus we have different portions of the same bed of different ages. Now if the sinking of the marsh be stopped for a time, the bed will become thicker in the portions left exposed, and if the sinking now changes in direction, so that the part that had previously gone down commences to rise, we should have the phenomenon of a bed, continuous throughout, with one portion overlying another, and separated from it by rock strata. These are exactly the conditions observed in splitting beds. While one side of the lake is sinking, and the peat marsh moving on in that direction, the other side may be rising,

By P. B. Venuto, E. T. Strom, S. A. Dixon, W. F. Johnson, T. C. Vogt

Prior to assessing potential for in-situ leaching, it is advantageous to identify the nature of the probable reactants in the ore horizon, including both the uranium species and those in the gangue material. We report mineralogical data on an areally-broad suite of samples from the Westwater Canyon Member of the Jurassic Morrison Formation in the Crownpoint area of the Grants Mineral Belt. Optical microscope, electron micro-probe, X-ray diffraction, spectroscopic and wet chemical analyses were conducted. In these samples, the uranium occurs predominantly as either coffinite or uraninite. The host rock is arkosic sandstone, comprised mainly of detrital quartz and feldspar. The minerals kaolinite and chlorite are present in claystone clasts and calcite occurs as a cement. Major trace elements include molybdenum, vanadium, iron, selenium and sulfur. Carbonaceous organic material is present in the ore and is intimately associated with the uranium mineral when it is coffinite. Geochemical, pyrolytic and 13C NMR analyses indicate organic material is probably a very mature, coaly-type kerogen derived from plant components.

Jan 1, 1982

By M. L. Fuller

IN connection with an investigation in this laboratory on the high-zinc side of the copper-zinc system, it was observed that well developed segre-gate structures of the Widmanstätten type were formed when a secondary phase precipitated from the solid solution of copper in zinc. This paper presents an analysis of the crystallographic relationship between the segregate and the solid solution matrix. The data to be presented are an interesting addition to the literature on segregate structures in that the plane of segregation is one of the less densely populated planes. In agreement with the generalization of C. H. Mathewson and D. W. Smith1 the plane of segregation in the matrix con-tains the direction of closest atomic packing of the lattice. Furthermore, the matrix and the segregate are both hexagonal close-packed, which has not been reported hitherto in the literature.2 The increasing com-mercial importance of zinc alloys containing copper makes this funda-mental study of value to the metallography of zinc alloys.

Jan 1, 1933

By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961

By R. W. Cahn, C. D. Graham

The rate of growth of a single grain growing into a strained aluminum single crystal, measured by the conventional heat-cool-etch technique, is shown to decrease with time at temperature. The growth rate measured by means of X-rays, with the sample continuously at temperature, is found to be linear. Evidence is presented to show that the decreasing growth rate obtained by the conventional technique is due to abnormal recovery in the strained grain, and that the recovery in turn results from the heating and cooling cycles, rather than from the effects of etching. The experimental apparatus is described in an appendix. FREQUENTLY, the rate of grain boundary motion during recrystallization is determined by heating a sample to a known temperature for a given time, cooling to room temperature, and etching to reveal the boundary position. The cycle of operations is repeated as many times as necessary to establish the rate of boundary motion. Although this heat-cool-etch technique has been used by a number of workers over a period of many years,&apos;-!&apos; other investigators have encountered difficulty with the method."&apos;. " They have attributed the erratic results to the effects of repeated heating and cooling, or of etching, or both, and have adopted an alternative experimental procedure in which a number of identical samples are employed, each sample being cooled and etched only once. This alternative method ove1.comes some difficulties, but introduces others. In particular, the incubation periods of the observed grains are unknown: any effect of crystal orientation on growth rate cannot be determined easily. A preferable method would be to measure the motion of a recrystallizing grain boundary with the sample at temperature without etching," but such measurements have in the past been restricted to nonmetals. This paper describes the construction and operation of a device, the goniometer furnace, with which the position of a moving grain boundary between a recrystallizing grain and the strained single crystal into which it grows can be measured by means of X-rays, with the sample maintained continuously at temperature. Goniometer Furnace The operating principle of the goniometer furnace is shown in Fig. 1. The sample, in the form of a bicrystal strip, is surrounded by a furnace, not shown in the sketch, and can be rotated about the two axes A and B which intersect at the point where the X-ray beam strikes the strip. The strip is oriented so that one of the two grains gives a strong Bragg reflection, which is detected by a suitably placed Geiger-Miiller counter coupled to a counting-rate meter When the strip is moved parallel to its own length in the furnace, arrow C, so that the X-ray beam strikes the second grain, there is in general no strong reflection. By noting the position of the strip at which the drop in Geiger counter reading occurs, it is possible to determine the position of the boundary. Measuring the change in boundary position with time at temperature gives the rate of growth of the recrystallizing grain. Details of the construction and operation of the goniometer furnace are given in the Appendix. Measurements showed that the temperature in the furnace was uniform within ±10°C over its working length of about 28 cm. The temperature at the measuring position, i.e., at the point where the X-ray beam struck the sample, was estimated to be constant within ±2oC. Using the goniometer furnace, the position of a stationary boundary could be measured with a reproducibility of ±0.3 mm. At elevated temperatures, 500" to 625"C, with the boundary in motion and the X-ray reflection less sharp, the estimated accuracy of each measured boundary position dropped to about ±1 mm. Experimental Results The test pieces were single crystals of 99.6 pet A1 —principal impurities 0.19 pet Fe and 0.12 pet Si— 1 mm by 1 cm in cross section and 6 to 10 cm in length, grown by the strain-anneal method. This relatively low purity material was used because of the difficulty encountered in producing strain-anneal single crystals of very high purity—99.996 pet—

Jan 1, 1957

By Ferid Kromer

Geography: The Tagtepe district of the Vilayet of Eskigehir is about 20 miles northeast of the city of Eskigehir (approximately midway between Ankara and Istanbul) in western Anatolia. The area is a mountainous one, the highest peak being Tagtepe Mountain (5200 ft) which is approximately in the center of the district. The mountains drop off to the deep valley of the Sakarya River on the north and to the plain of Eskigehir on the south. FERID KROMER, Junior Member AZME, is a Consulting Mining Engineer and General Manager, Bagtag Turk Maadin Ltd., Istanbul, Turkey. New York Meeting, February 1950. TP 2629 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received Dec. 29, 1948. For the most part, the watershed is on the northern side of the mountain barrier, draining into the Sakarya River, which in turn empties into the Black Sea midway between Zonguldak and the mouth of the Bosphorus. The approximate area covered by the Tagtepe district is shown in fig. 1. Transportation to shipping points is available via the Istanbul-Ankara railroad. The station on this line nearest the mining district is Alpikoy station, about 20 miles by road southwest of Tagtepe Mountain. Interior roads within the district are poor. Being of dirt, the winter rains and snows render them almost impassable for trucks from about the middle of December until the end of March, thus presenting a considerable transportation problem. However, the roads from the Bagoren and Tagtepe chromite mines to the railroad shipping point at Alpikoy station have recently been repaired and will be maintained for all-weather truck transportation. Detailed climatic data are not available. However, in general the spring, summer, and early autumn months are dry, and good weather may be expected from May until early November. Then the winter rains commence, and heavy snow is usual during January and February. Geology: The mountainous structure of Tagtepe belongs to basic rocks of serpentine (Variscan Orogeny) which is in contact with Paleozoic schists at west, and an Oligocene outcrop of red clays in Margi-Sepetci region (see fig. 1) at southeast. The northwest and southwest borders of Tagtepe district are, respectively, surrounded by Paleozoic schists and pebbly gray and yellow Neogene clays. More recent formations of alluviums overlay the plain of Eskigehir. Dark basic rocks of trachytes with hornblende are visible on Turkmenbaba Mountain, at the west of Tagtepe. Mineral Occurrences: Chromite: the most important mineral found in any quantity in the Tagtepe district. The alignment of the deposits of chromite is in general along the line Bagoren-Tagtepe (see fig. 1). The first mines in the area were those of Tagtepe and Bagoren, which were developed over 20 years ago with Swedish capital. Other deposits of chromite, more recently discovered and so far of less importance, are being worked at Kurucor, Komurcu, Gelinmezari, and Lacin (see fig. 1). Deposits average generally between 46 and 48 pct chromic oxide, with the exception of the Bagoren mine which averages 44 pct. However, a new lode, very recently plotted, in the Tagtepe mine averages 50 pct Cr,O,, 4.6 pct SOz, and 7 pct FeO. Geological character of the chromite occurrences in the Tagtepe mine may be considered typical of most chromite lodes in this area. The indications are that the formations of ore lenses are developed by the segregation of chromite crystals intruded into the serpentinized rock, and exposed later to tectonic movement within the zone of crystallization. All lenticular masses are more or less regular in shape and follow each other in southeast-northwest direction and dip generally 70" NE. Ore lenses do not seem to persist in depth, average depth of two lenses is 60 ft below surface. Three lodes .have been mined as open-pit. The average dimensions of individual lenses are as follows: pitch length, 100 ft; breadth, 27 ft; and width, 20 ft. The lenses and their enclosing rocks are broken by parallel fractures in approximately east-west direction. These joints are filled, except in one lode, with cementing material, which gives to the ore a

Jan 1, 1951

By Richard J. Fruehan

ThE thermodynamic activities of nickel and chromium in liquid Ni-Cr alloys have not been previously reported. There have been several investigations on the solid alloys.1-3 In the present investigation the activity of chromium in liquid Ni-Cr alloys at 1600° C was determined by the use of the following galvanic cell, The use of galvanic cells employing solid oxide electrolytes for determining the activity of metals in solid alloys was first demonstrated by Rapp and Maak4 on Cu-Ni alloys between 700° and 1000°C. Recently Schwerdtfeger5 tested the performance of the ZrO2(CaO) electrolyte at 1600°C and found it satisfactory for oxygen pressures as low as 10"12 atm. He also demonstrated the use of solid oxide electrolytes for determining the activities in liquid metal systems in measuring the activity of manganese in Fe-Mn alloys at 1500°C. Extensive investigations have been carried out in this laboratory, exploring the oxygen partial pressure lower limit at which ZrO2(CaO) electrolyte can be used satisfactorily in oxygen galvanic cells at 1600°C. In a paper to be published at a later date,9 it is demonstrated conclusively that ZrO2(CaO) exhibits insignificant electronic conductivity at oxygen pressures down to about 3 x 10"13 atm which is lower than the oxygen partial pressure in equilibrium with Cr-Cr2O3 at 1600°C. Therefore, the activity of chromium can be related to the measured reversible electromotive force of the cell in the present investigation since no electronic short circulating will occur. Fig. 1 is a schematic diagram of the cell used. The Cr-Cr2O3 electrode was made of equal weights of chromium and Cr2O3 powders which were mixed and packed into a recrystallized alumina crucible. A Pt-wire lead was embedded into the Cr-Cr2O3 compact to insure good contact. A ZrO2(CaO) crucible, supplied by the Zirconium Corp. of America, contained the Ni-Cr melt equilibrated with solid Cr2O3. The ZrO2(CaO) crucible was placed on the Cr-Cr2O3 electrode and additional Cr-Cr2O3 mixture was packed around it. Contact with the Ni-Cr alloy was made with a Cr2O3 tube, which is a weak electronic conductor. A platinum wire lead was attached to the Cr2O3 tube. The galvanic cell was lowered slowly into the hot zone of the furnace tube in order to avoid too large a thermal shock which could break the ZrO2 (CaO) crucible. The furnace was con- tinuously flushed with purified argon during the experiment. The temperature was measured with a Pt-Pt/10 pet Rh thermocouple and maintained at 1600° ± 5°C. The electromotive force was measured with a recording potentiometer. The furnace was turned off when measurements were being made in order to avoid induction effects and the reversibility of the cell was demonstrated in the usual manner. The electromotive force was measured several times over a period of approximately 1 hr. During that period the electromotive force remained constant within ± 3 pet and did not continuously drift in any one direction. After the experiment the alloys were analyzed for chromium in the usual manner. The measured electromotive forces of the cell at 1600°C, (2912°F), are listed in Table I. The activity of chromium, with solid pure chromium as the reference state, (a), was calculated using Eq. [l], , n F E I, n lna RT- U] where E is the measured electromotive force, F is the Faraday constant, and n is equal to 3, the number of equivalents per mole, (nF/RT = 18.59 volts&apos;1 at 1600°C). The resulting activities are listed in Table I. The activity of chromium relative to pure liquid chromium was also calculated. The free energy of fusion of chromium at 1600° C was calculated using

Jan 1, 1969

By Ferid Kromer

Geography: The Tagtepe district of the Vilayet of Eskigehir is about 20 miles northeast of the city of Eskigehir (approximately midway between Ankara and Istanbul) in western Anatolia. The area is a mountainous one, the highest peak being Tagtepe Mountain (5200 ft) which is approximately in the center of the district. The mountains drop off to the deep valley of the Sakarya River on the north and to the plain of Eskigehir on the south. FERID KROMER, Junior Member AZME, is a Consulting Mining Engineer and General Manager, Bagtag Turk Maadin Ltd., Istanbul, Turkey. New York Meeting, February 1950. TP 2629 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received Dec. 29, 1948. For the most part, the watershed is on the northern side of the mountain barrier, draining into the Sakarya River, which in turn empties into the Black Sea midway between Zonguldak and the mouth of the Bosphorus. The approximate area covered by the Tagtepe district is shown in fig. 1. Transportation to shipping points is available via the Istanbul-Ankara railroad. The station on this line nearest the mining district is Alpikoy station, about 20 miles by road southwest of Tagtepe Mountain. Interior roads within the district are poor. Being of dirt, the winter rains and snows render them almost impassable for trucks from about the middle of December until the end of March, thus presenting a considerable transportation problem. However, the roads from the Bagoren and Tagtepe chromite mines to the railroad shipping point at Alpikoy station have recently been repaired and will be maintained for all-weather truck transportation. Detailed climatic data are not available. However, in general the spring, summer, and early autumn months are dry, and good weather may be expected from May until early November. Then the winter rains commence, and heavy snow is usual during January and February. Geology: The mountainous structure of Tagtepe belongs to basic rocks of serpentine (Variscan Orogeny) which is in contact with Paleozoic schists at west, and an Oligocene outcrop of red clays in Margi-Sepetci region (see fig. 1) at southeast. The northwest and southwest borders of Tagtepe district are, respectively, surrounded by Paleozoic schists and pebbly gray and yellow Neogene clays. More recent formations of alluviums overlay the plain of Eskigehir. Dark basic rocks of trachytes with hornblende are visible on Turkmenbaba Mountain, at the west of Tagtepe. Mineral Occurrences: Chromite: the most important mineral found in any quantity in the Tagtepe district. The alignment of the deposits of chromite is in general along the line Bagoren-Tagtepe (see fig. 1). The first mines in the area were those of Tagtepe and Bagoren, which were developed over 20 years ago with Swedish capital. Other deposits of chromite, more recently discovered and so far of less importance, are being worked at Kurucor, Komurcu, Gelinmezari, and Lacin (see fig. 1). Deposits average generally between 46 and 48 pct chromic oxide, with the exception of the Bagoren mine which averages 44 pct. However, a new lode, very recently plotted, in the Tagtepe mine averages 50 pct Cr,O,, 4.6 pct SOz, and 7 pct FeO. Geological character of the chromite occurrences in the Tagtepe mine may be considered typical of most chromite lodes in this area. The indications are that the formations of ore lenses are developed by the segregation of chromite crystals intruded into the serpentinized rock, and exposed later to tectonic movement within the zone of crystallization. All lenticular masses are more or less regular in shape and follow each other in southeast-northwest direction and dip generally 70" NE. Ore lenses do not seem to persist in depth, average depth of two lenses is 60 ft below surface. Three lodes .have been mined as open-pit. The average dimensions of individual lenses are as follows: pitch length, 100 ft; breadth, 27 ft; and width, 20 ft. The lenses and their enclosing rocks are broken by parallel fractures in approximately east-west direction. These joints are filled, except in one lode, with cementing material, which gives to the ore a

Jan 1, 1951

By C. S. Smith, K. K. Ikeuye

In an earlier paper1 one of the authors called attention to the significance of the relative free energies of grain boundaries and interphase boundaries in alloys in determining the shape and distribution of micro-constituents. The ratio of the interphase and inter-crystalline boundary energies (that is, —?12, where ?12 is the energy of the interface between a crystal of phase 1 and a crystal of phase 2, and ?11 is the energy of the boundary between two crystals of phase 1) will be denoted by F. It is this ratio that determines, by the simple triangle of forces relation, the dihedral angle, ?, of phase 2 where it adjoins a boundary between two grains of phase 1. On a metallographic sample various angles are actually obtained because of the random orientation of the plane of observation, but the statistically most frequent angle is the true one. These basic principles were discussed in detail in the earlier paper. The experiments described below show the effect of both composition and temperature on ? and T for some alloys containing a liquid phase, and provide data on the rate of approach to the equilibrium angles in both solid and liquid phases. All the alloys were melted in a graphite crucible and cast into ingots 3/4 by 11/8 in. cross-section. Some of the aluminum alloys consisted of two immiscible liquids from which uniform castings could not be obtained. The amount of liquid phase varied locally to a considerable extent and the analyses were meaningless. Nevertheless, the composition of the liquid would not differ from that in an alloy of the intended gross composition, and the synthetic composition of the alloys was therefore used in considering the surface energy results. The ingots were given initial deformation by cold-rolling to 50 pct reduction, annealed, and given a second 50 pct reduction prior to cutting into small samples for heat treatment at the times and temperatures subsequently reported. The resulting micro-samples were carefully prepared metallographically and examined at magnifications of 650, 1280, or 2500. The objectives used were 21X, 0.40 NA (dry); 41X, 0.65 NA (dry); and 80X, 1.40 NA (oil emulsion). The appropriate angles were measured by rotation of the stage of a Bausch and Lomb metallograph to align the appropriate boundaries successively with a cross-hair in a micrometer eyepiece. About 250 angles were measured on each phase. Though the angles were read to 1°, the accuracy is probably not above 3°, because of uncertainty in setting the cross-hair tangent to the sometimes curved boundary. The corners of very small particles, particularly in early stages of adjustment after cold-rolling, were difficult to measure and the results were slightly dependent on the magnification used (compare Fig 1-C and 1-D). With particles of larger size and more nearly equilibrium shape, magnification made no difference (vide Fig 1-F and 1-G). The measured angles were grouped in 10° intervals (5° if ? was less than 20°) and plotted in bar

Jan 1, 1950

By W. A. Backofen, R. L. Fleischer

Single crystal, bicrystal, and polycrystal tensile tests of aluminum at 4.2°K, 77°K, and 300°K have been used to examine the role of grain boundaries in the deformation process. Results indicate that a grain boundary may affect the extent and slope of easy glide. The stage II hardening rate, on the other hand, is independent of the presence or absence of grain boundaries. This conclusion allows the size of the region of multiple slip caused by an incompatible grain boundary to be determined. For the size of bicyystal sample used in this study, multiple slip occurs in about half of the cross section. PREVIOUS studies of the stress-strain characteristics of bicrystals of face-centered-cubic metals have been limited to aluminuml-5 at room temperature. Recent results, however, indicate that the stress-strain curves of single crystals of such metals may be separated into at least three stages6 in which different deformation processes are occurring7 provided testing is done at sufficiently low temperatures.&apos; Since for aluminum a well-defined stage II develops only below room temperature, previous studies have not been able to relate effects of grain boundaries to all of the three stages of deformation. It is therefore to be expected that low-temperature deformation of aluminum single crystals and bicrystals should clarify the effects of grain boundaries on the different processes of deformation. EXPERIMENTAL PROCEDURE Single crystals and bicrystals were grown from the melt by the standard techniqueg with aluminum reported by Alcoa to be 99.993 pct pure. Ridges in the boat were used to guide the grain boundary during growth, assuring that the boundary would bisect the sample.10 The rate of furnace motion during growth was 1.0 cm per hr. During growth zone purification resulted, as evidenced by the ability of the first material to freeze to recrystallize at room temperature following severe deformation. Samples were approximately 4.4 X 6.6 mm in cross section and 103.5 mm in length between grips. Samples were annealed at 635" i 5°C for 40 hr and furnace cooled over a 7-hr period. They were then electropolished in a solution of 5 parts methanol to 1 part perchloric acid at a current density of 15 amp per sq dm for about 30 min at temperatures below 0°C. Tensile testing was performed at 295" (room temperature), 77" (sample in liquid nitrogen), and 4.2"K (sample in liquid helium) on the hard-type machine indicated schematically in Fig. 1. The machine con- sists basically of a tube surrounding a rod; one end of the sample is attached to each member, and the rod is pulled up the tube to extend the sample. The rod is rigidly mounted and is moved vertically by a system described by asinski." The pulling force is measured continuously by an electrical strain gage load cell, and the relative displacement of the tube and rod is also recorded continuously by a soft cantilever beam with electrical strain gages. Maximum stress and strain sensitivities were ±2g per sq mm and * 3-10-5. In all tests the strain rate was approximately 5.10-5 per sec. The thin wires in the tensile apparatus introduce softness, which may be corrected for, however, by measuring load vs displacement with the sample replaced by an elastic member. For loads greater than 15 kg the spring constant is 1.875.106 g per cm. The flexible wires also served to reduce substantially the large shearing forces which may arise in the case of grips having horizontal rigidity.&apos;&apos; As in any gripping system, however, bending moments will arise in the course of deformation by single slip. Engineering stress, s = (load)/(original cross-sectional area), and strain, E = (increase in length)/ (original length), are used for stress-strain curves unless otherwise indicated. Tables list resolved shear stress, T=mo and shear strain ? = dm, where m is the usual Schmid resolved shear stress factor for the primary slip system at the start of deformation. The first group of samples to be described forms an isoaxial set, all of the crystals making up the single crystals or bicrystals having the same tensile axis, the orientation of which is indicated by the cross in Fig. 2. For this orientation the primary slip plane and slip direction make angles of 45 deg with the tensile axis and the Schmid factor m has its maximum possible value of 0.5. Rotations about the tensile axis are indexed by means of an angle 0 between the small-area surface of the samples and the projection of the primary slip direction onto the cross section, as defined in Fig. 3. In single crystals, values of 0 were 0 and 90 deg, while in bicrystals 0 values were (0 deg, 180 deg), (90 deg, 270 deg), and (0 deg, 90 deg) as indicated in Fig. 4.

Jan 1, 1961

By C. C. Templeton, J. C. Rodgers

A key step in feed water treatment for generating wet steam for thermal oil recovery is the removal of calcium and magnesiunt hardness by cation-exchange series softening. Knowing the solubility of any scale forming salts in brines at elevated temperatures is necessary for fixing the level to which the feed water must be softened. Such calcium sulfate solubility data, previously not available above 392F, were determined by the authors in a flow equilibrium apparatus mud will be reported elsewhere. These data were used to develop a method for predicting the solubility of anhydrite in hot water or steam droplets for saturated steam pressures as high as 2,000 psig (637F). (The calcium sulfate solubility product is represented by a combination of two factors, one reflecting the effects of ionic strength and the other accounting for the effects of complex ion formation in either calcium-magnesium-rich or sulfate-rich brines.) The method is applied to a calcium-magnesium-rich brine If moderately high salinity from a pilot hot-water flood, I nd to several sulfate-rich, low-salinity feed waters and l lowdown (cooled steam droplets) samples from steam s ak operations. The predicted calcium hardness levels corresponding to the calcium sulfate solubilities agreed reasonably well with the results of laboratory solubility determinations run on the field samples. Further testing of the method is needed for brines of other composition classes. Existing field cation exchange softeners in the cases tested are performing adequately since all the samples were found to be undersaturated with respect to calcium sulfate at their operating temperatures. Introduction Prevention of scaling caused by precipitation of calcium sulfate (anhydrite) is of considerable concern in connection with thermal recovery processes using wet steam or hot water. To avoid anhydrite precipitation in a heated system, an engineer must keep the product of the calcium and sulfate concentrations in the water or steam droplets below the value of the solubility product of anhydrite for the temperature and brine composition in question. Usually it is most practical to keep the concentration product lower than the solubility product by keeping calcium low in the presence of high sulfate, or by keeping sulfate low in the presence of high calcium. This can be done by a choice of combinations of natural waters and water treatment processes (such as series cation exchange softening to remove calcium). Until recently, few anhydrite solubility data, particularly for solutions containing other salts, were available for temperatures above 392F (211 psig steam); Marshall, Slusher and Jones&apos; studied the CaS0,-NaCI-H,O system up to 392F and surveyed the work of previous investigators. To model natural brines, one needs to study the solubility of anhydrite in aqueous solutions of sodium chloride, sodium sulfate, calcium chloride, magnesium chloride and their mixtures. Since steam pressures as high as 2,000 psig (637F) may be involved in thermal oil recovery projects, a solubility study was conducted between 482 and 617F.&apos; Discussed in this paper is the application of these data to the prediction of anhydrite precipitation in some practical steam soak and hot-water injection projects. Any simple method for predicting the solubility of an inorganic compound over a wide range of temperatures and solution compositions must be based on some assumptions, and therefore must yield approximate results. On the one hand, natural brines contain too many ionic species for all to be included in a simple scheme; on the other hand, there is no adequate theoretical basis for the exact prediction of solubility in even simple solutions of mixed electrolytes. However, it is possible at a given temperature to base a reasonable prediction scheme on two phenomena:&apos;-&apos; the increase in solubility with increasing total concentrations of all ions (as measured by the ionic strength; see the Appendix), and an increase due to formation of cornplexes between calcium ions and sulfate ions and between sulfate and magnesium ions. Stiff and Davis&apos; developed such a scheme for predicting the solubility of gypsum (CaSO, ¦ 2H,O) in brines at temperatures u~ to 212F. However, for the higher temperaturei of present interest, the stable solid phase is anhydrite (CaSO,). This study involves a two-part method for predicting anhydrite solubility products. First, one predicts a value K, for a given ionic strength I and a given temperature T corresponding to mo./msr, = 1 from data of the CaS0,-NaCI-H,O system. Second, one determines a group of factors F .= F(Ca) • F(Mg) • F(SO,), where the individual factors account for increases in the solubility product due to complex formation by high concentrations, respectively, of calcium, magnesium and sulfate. Combining the two parts, one obtains the solubility product in molalities as

Jan 1, 1969