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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' 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.' 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:'-' 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' 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

By John Chipman

The concentration of a solute in a dilute ),zetallic solution may be measured by any of several parame- ters including weight percent, atom fraction, atom ratio, and lattice ratio. The ratio of filled to unfilled interstitial sites is useful for interstitial solutes. A variable 2 proportional to this ratio is used as a measuve of concentration. For component 2 irz a bitzary solution z2 = n2/Ym - nz/b) where b is the numberber of interstitial sites per lattice atom. For a t~lul-ticortzporzent solution this becomes zz = n2/(nl + Cvjnj) in which Vj = - l/b for an interstial solute and +1 for a substitulional solute. In the infinitely dilute solution the activity of an interstitial solute 2 is proportional lo z2. At finile concentration the departure from this limiting law is expressed us an activity coefficient, his coefficient is a function of concentra1io)z expressed as tevactiolz coeffcient 8; is analogous to the jark~iliar e£ bul is found to be independent of concentvation in certain solutions for which data are available. It is found that the same equations may be used to express the activity of a nonmetallic solute, sulfur, in liquid solutions of iron containing other solutes, both metallic and nonmetallic. For a nonmetallic solute or for one which strongly increases the actiuity of sulfur, it is convenient to assign arbitvarily a value vj = — 1. When this is done the derivative is found to be constant in each of the ternary solutions studied. The activity coefficient of sulfur in a complex liquid iron solution may be expressed as where nk is a second-order cross product determined in the quaternary solution Fe-S-j-k. The equation is used to calculate tlze activity of sulfur i)z three sevetl- component solutions. IN thermodynamic calculations concerning dilute solutions it is unnecessary to invoke laws and relations which extend across the concentration range to include concentrated solutions. In most binary metallic systems, as arkeen&apos; has recently pointed out, there exist two terminal composition regions of relatively simple behavior, connected by a central region of much greater complexity. When the solute is a nonmetal there is only one such region and in many systems the concentration range is extremely limited. It is the purpose of this paper to suggest a method for the calculation of activities in such a terminal region in which one or more solutes are dissolved in a single solvent of predominantly high concentration. HENRY&apos;S LAW In the usual textbook statement of Henry&apos;s law, concentration is stated in mole fraction. This has the advantage that it makes Henry&apos;s law thermodynamically consistent with Raoult&apos;s law. Since all measures of concentration at infinite dilution are related by simple proportion it follows that mole fraction, molality, atom ratio, weight percent, or any other unit of concentration can be used with the appropriate constant. At finite concentrations, however, calculations based on the law depend upon the unit employed. Deviations from Henry&apos;s law at finite concentrations depend upon the composition variable employed. They are evaluated in terms of activity and interaction coefficients2 which have become familiar features of metallurgical thermodynamics. It is the purpose of this paper to propose a measure of concentration for metallic solutions containing interstitial or nonmetallic solutes by means of which the calculation of activities in complex solutions may be simplified. The discussion will be restricted to free-energy interaction coefficients3 typified by Wagner&apos;s c|a BINARY SOLUTIONS The several measures of concentration which are to be considered are shown in line a of Table I. The corresponding activity coefficients are in line b and the deviation coefficients, sometimes called self-interaction coefficients, are in line c. Henry&apos;s law simply states that the activity coefficient approaches a constant value at infinite dilution. By adoptihg the infinitely dilute solution as the reference state and defining the "Henrian" activity as equal to the concentration in this state, the activity coefficient is always unity at infinite dilution. This convention is far sim~ler and more useful in dilute solution than emploiment of the &apos;Raoultian" activities and it will be used in the following discussion. The several definitions and equations of Table I will be referred to by means of their coordinates in the table. Early observations of deviations from Henry&apos;s law in metallic solutions were shown graphically4 rather than analytically. For the case of sulfur in liquid iron5 the slope of a plot of logfs vs (%S) was constant in the range 0 to 4.8 pct S, indicating constancy of eh2&apos; in Ic. He was proposed by wagnerz and has been widely adopted. The a function of IIIc recently employed by ~arkenl was designed specifically for dilute solutions. Darken has shown that the value of a12 remains essentially constant for many binary solutions within a substantial range of compositions. The atom ratio is directly proportional to the molalitv.<, a conventional measure of concentration. IVb and C served as the basis for smith&apos;s6 classic studies of

Jan 1, 1968

By M. J. Marcinkowski, K. S. Raghavan, A. S. Sastri

A detailed transmission electron microscopy investigation was carried out in connection with a manganese Hadfield Steel. At small plastic strains, numerous individual intrinsic stacking faults are observed. With increased plastic deformation, the stacking faults thicken into twin lamellae which in turn subdivide the original austenite matrix into smaller domains. The twin boundaries act as strong barriers to subsequent dislocation motion and is in a sense equivalent to grain refinement. It is this "grain refinement" which is believed to be the cause of the very high work hardening rates in the Hadfield Steels. In many cases, especially where an hcp phase is the stable one at low temperatures, the stacking fault energy in fcc metals and alloys decreases with decreasing temperature.&apos; Since stacking faults of the intrinsic type are precursors of both twins as well as the hexagonal close packed structure, both of these entities should become more frequent as the temperature of a fcc crystal is lowered. In the case of the twin, there is no chemical driving force for its formation and it is generally necessary to provide the required driving force by an applied stress, i.e., strain energy. In the case of the hcp structure the transformation from the fcc modification can occur spontaneously (marten-sitically) since a decrease in chemical energy does in fact occur; however, an applied stress will provide an even greater driving force toward complete transformation. Since the transformation products mentioned above occur in an inhomogeneous manner throughout the crystal and since these can act as potential barriers to further plastic deformation2 marked strengthening effects can be anticipated. Also because metal and alloy strenghening is in general proportional to the shear modulus, these effects should be greatest in steels of the austenitic type (y), i.e., the fcc types. Perhaps the two most important steels in this category are the austenitic stainless steels and the Hadfield manganese steels. Both may be quenched from elevated temperatures so as to retain the austenitic states characteristic of those temperatures. The effect of subsequent deformation at lower tem- peratures has a profound effect on the stress-strain curves of these alloys. In particular Fig. 1 shows the compressive stress-strain curves obtained with an 18-8 stainless steel which was quenched from 1850°C after annealing for 1 hr so as to produce all y. As the temperature is lowered, the work hardening rate increases markedly. Although some hcp or c mar-tensite can be generated by plastic deformation as the temperature is lowered,~ it is believed to be a transition phase4 and most of the martensite produced is of the bcc or a variety.3 It is this stress induced martensite which gives rise to the very low initial work hardening at 77°K as can be seen in the stress-strain curve in Fig. 1. Similar low initial work hardening rates have been observed in the stress induced Ni-Ti martensites.5 Fig. 2 shows that an even more rapid rate of work hardening occurs in the Hadfield steels treated in the same way as that described for the 18-8 stainless steels a; the temperature is lowered. It is this ability to work harden to such high stress levels that makes the Hadfield steels particularly suitable for armor plate and heavy construction equipment. However, unlike the case of Fig. 1, no initial low rate of work hardening is observed in any of the curves in Fig. 2. Thus the stress induced formation of any low energy martensite phase in any significant quantity must be ruled out. This observation is in accord with the X-ray findings of Otte.~ On the other hand, small quantities of the E phase have been observed by other investigators using transmission electron microscopy (TEM) above Even more significant was the fact that large numbers of deformation twins were observed in the deformed Hadfield steels,678 which were postulated to be one of the reasons for the high work hardening ability of this class of steels.8 It is the purpose in what follows to discuss a series of experimental observations pertaining to the stress induced transformation in a Hadfield steel and to formulate a dislocation mechanism which adequately accounts for the observed results. EXPERIMENTAL PROCEDURE The stainless steel used to obtain the curves shown in Fig. 1 was of the AISI Type 303 containing approximately 18.0 pct Cr and 8 pct Ni. On the other hand, the Hadfield manganese steel used to obtain the curves shown in Fig. 2 contained between 1.00 to 1.25 pct and 11.5 to 13.5 pct Mn. In all cases the samples were in the form of compression cylinders 0.220 in. in diam and 0.370 in. long. Prior to testing the samples were annealed for a hr at 1050°C and rapidly quenched into a brine solution. This treatment was sufficient to preserve the y phase for subsequent testing at lower temperatures. All samples were compressed in an Instron testing machine using a cross head speed of 0.02 in.

Jan 1, 1970

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid binary and ternary Fe-Ni-Co alloys has been measured by the Sieverts&apos; method between 1550°and 1700°C. Solubility data and standard free energzes and enthalpies of solution for nitrogen in the alloys are presented. Interaction parameters are discussed and presented for binary and ternary alloys. MOST of the studies of nitrogen solubility in liquid metals have been directed toward the dilute alloys of iron. Several of these investigations have included measurements of the nitrogen solubility in Fe-Ni al10s&apos;- and in Fe-Co alloys.435 There has been some work, however, that has extended across the e-i-" and F-CO" binaries. This investigation was undertaken to determine the nitrogen solubility in both binary and ternary alloys of the Fe-Ni-Co system. It was also hoped that the differences between earlier studies might be resolved. EXPERIMENTAL METHOD This investigation was made using a Sieverts&apos; apparatus described previously." The nickel (99.85 pct) and cobalt (99.9 pct) were obtained from Sherritt-Gordon Mines, Ltd., and the iron (99.95 pct) was Fer-rovac-E obtained from Crucible Steel Co. Recrystal-lized alumina crucibles were used throughout the entire investigation with no evidence of crucible-melt reaction. Melt temperatures were measured with an optical pyrometer and the temperature scale calibrated against the melting points of the three pure metals. The emissivity of the melt was assumed to be a linear function of composition for all alloys, as has been shown for Fe-Ni alloys.lZ The emissivity of the pure metals at 1600°C were taken as 0.43 for iron, 0.44 for cobalt, and 0.45 for nickel. Using these emissivities, the trans mis sivity of the system was found to be 0.51 i 0.01. The Sieverts&apos; method was used for this study and followed the procedures outlined previously.l&apos; The individual metals were weighed to give about 100 g of alloy. The alloys were melted in the crucible under a partial pressure of argon. The system was evacuated, and the "hot volume" was measured with argon. To avoid the errors caused by vaporization, the melt was held under vacuum only long enough to ensure that all of the gas in the system had been removed. The influence of any small amount of vaporization on the "hot volume" was shown to be negligible by measuring the "hot volume" after a run. This measurement agreed with that made at the start of the run within the implicit error, 0.2 cc, caused by the limitations in accurately reading the buret. The solubility-pressure relationship was measured in the pure metals and in several alloy compositions throughout the ternary system. These measurements were made by admitting measured amounts of nitrogen to the system, and then determining the equilibrium nitrogen pressure above the melt. This method has the distinct advantage of higher accuracy, particularly at lower pressures, than measurements made by withdrawing gas from the system to reduce the pressure after determining the solubility at 1 atm nitrogen pressure. This latter method has a practical lower limit of about 0.4 atm where an increased error is encountered because the buret must be emptied to permit further measurements at lower pressures. By determining the relation between apparent solubility and pressure, it was possible to make a good estimate of the initial nitrogen content of the metal from the intercept of the solubility curve extrapolated to zero pressure.11 DISCUSSION The solubility data corrected to 1 atm nitrogen pressure are summarized in Table I. The reported solubility has been corrected for the initial nitrogen content of the alloys. The initial nitrogen contents fell between 0.0002 and 0.0010 wt pct, and were lower in the iron and nickel than in the cobalt. Sieverts&apos; law was obeyed in all alloys at pressures up to 1 atm. Examples of this behavior are shown in Fig. 1. The reaction for solution of nitrogen is Taking the standard state as 1 wt pct N in the alloy and the reference state as nitrogen at infinite dilution in the alloy, and noting the adherence to Sieverts&apos; law, K becomes the solubility of nitrogen in the alloy at 1 atm pressure. Thus the solubility data of Table I were used directly to calculate the standard free energy for the solution reaction. These results are also presented in Table I. The enthalpy of solution is also summarized in Table I as calculated from a form of the van&apos;t Hoff relation: Iron-Nickel System. The data for the solubility of nitrogen in liquid Fe-Ni binary alloys is presented in Fig. 2 along the with data of aito, Schenck et al.,&apos; and Humbert and 1liott.l&apos; The data for studies of nitrogen solubility in Fe-Ni alloys containing less than 20 pc t i&apos;- are not presented in Fig. 2, although they are in good agreement with the present work. The results of this study are in good agreement with Schenck

Jan 1, 1967

By R. M. Waterstrat, E. C. van Reuth

BINARY- alloy phases having the A15-type crystal structure have been described as occurring at a simple and more or less invariant stoichiometric composition (A3B) which corresponds to the relative number of atoms occupying each of the two crystallographi lattice sites in this structure.1,2 It is frequently assumed, therefore, that each crystallographic site is occupied exclusively by one kind of atom. In most cases, however, there have been insufficient experimental data to establish whether atomic ordering is, in fact, complete. Recent studies have shown that binary A15-type phases are sometimes stable over an appreciable composition range3&apos;&apos;* and, occasionally, the composition range of stability does not even include the "ideal" A3B stoichiometric composition.5-7 We have observed the existence of nonstoichiometric A15-type phases in the binary systems Cr-Pt and Cr-Os. This has not been reported in previous work on these alloy systems.1,8-11 A series of alloys, each weighing approximately 30 g, was prepared by are-melting in an Ar-He atmosphere using 99.999 pct Cr, 99.999 pct Os, and 99.99 pct Pt as starting materials. Each alloy was melted four times with a total weight loss of less than 1 pct. The stoichiometric (A3B) alloys were sealed in evacuated quartz tubes and annealed at 1200°C for periods of time ranging from 3 days to 2 months. Examination of the alloy microstructures revealed that little change had occurred over this time interval and it was therefore assumed that the microstructures were fairly representative of equilibrium conditions. No evidence of contamination was observed although there was apparently some loss of chromium which was confined to a thin layer at the surface of the specimens. The quartz tubes were quenched from the annealing temperature into cold water. X-ray diffraction and metallographic examination of the stoichiometric alloys revealed an estimated 10 to 30 pct of second phases which were tentatively identified as phases previously reported in these binary-alloy systems.8-11 A second series of alloys was prepared by mixing -325 mesh metal powders having a nominal purity of 99.9 pct and compressing these mixed powders in a cylindrical die at a pressure of 43,000 psi. These alloys, each weighing 15 g, and some of the arc-melted alloys were annealed in a high-temperature vacuum furnace heated by tantalum strips at a pressure of 10-8 Torr and were rapidly cooled by turning off the furnace power. X-ray and metallographic examination of both series of alloys served to establish the composition ranges of the A15-type phases. Although some chromium losses occurred during the vacuum annealing, they were largely confined to a thin layer on the outer surfaces of the samples. It was established that the A15 phases occur in the Cr-Pt system at 21 ± 1 at. pct Pt after 1 week at 1200°C and in the Cr-Os system at 28 ± 1 at. pctOs after 1 day at 1400°C (see Table I). We also observed that an arc-melted stoichiometric (A3B) alloy in the Cr-Ir system was single-phase (A15-type) in the "as-cast" condition in agreement with previous work.8,13 In addition we obtained a sample of the Cr-Os A15-type phase from Argonne National Laboratory. This alloy contained less than 1 pct second phase12 and was submitted to a density measurement. The density measurement yielded a value of 11.14 g per cu cm in comparison to a theoretical value of 11.25 g per cu cm calculated using the observed lattice constant (4.6806Å) of this alloy. The uncertainty in measurement was 0.1 pct but the sample may have contained some cracks or minor imperfections which could account for the low experimental value. We have also studied the atomic ordering in these phases by means of integrated line intensity measurements using thick, flat, rotating powder samples and CuK a radiation in an X-ray diffractometer. We have obtained order parameters of 0.90 for the Cr-Pt phase, 0.89 for the Cr-Ir phase, and 0.64 for the Cr-Os phase using the formula: where s is the usual Bragg and Williams order parameter, ra is the fraction of chromium atoms in A sites, and FA is the fraction of chromium atoms in the alloy. The values obtained are estimated to be accurate within ±4 pct. If the unusually small value for the order parameter of the Cr-Os A15 phase were due to the existence of lattice vacancies on the "B-atom" sites, then a density of 10.04 g per cu cm would be expected in contrast to the observed value of 11.14 g per cu cm. We, therefore. conclude that the fraction of lattice vacan-

Jan 1, 1967

By George S. Ansell, John B. Hudson, Stephen A. Koffler

The permeability of hydrogen through the a phase of palladium has been measured by a low pressure permeation technique under conditions such that bulk diffusion was the rate-controlling process. The observed permeability is described by the equation: J = 1.80 x 1O-3 P½exp(-3745)/RT) cc(stp)/sec/cm2/en over a range of hydrogen pressure, P, from 2.9 x 10-5 m Hg to 5.0 x 10-3 cm Hg, and over a temperature range, T, from 300" to 709°K. The fact that the permeability shows a square root dependence on pressure and a reciprocal dependence on thickness was taken as evidence that bulk diffusion, rather than surface reactions, was the rate-controlling process. The permeability data were used in conjunction with the solubility data of Salmon et al., to determine the diffusivity of hydrogen through palludium as: D = 4.94 x 10-3 exp(-5745/RT) cm2/sec There was no influence of sub structural defects observed over the temperature range employed. From the permeability data obtained, coupled with grain size measurements, it was concluded that the ratio of grain boundary diffusivity to bulk diffusivity was less than 105 over the range of temperature investigated. THE diffusive mass transport of hydrogen in the a phase of palladium has been studied previously by numerous investigators.&apos; In spite of the large amount of attention this system has received, there is not good agreement between the results obtained in different investigations.&apos; This is due in part to the fact that the mass transport was surface-limited during some of these studies, rather than being diffusion-controlled3-5 The reason for the disagreement in other cases is not clear. These studies made use of such techniques as rate of absorption from solutions6 and gases,&apos; electrochemical potential,8 time lag,&apos; and permeation10,11 to determine the mass transport behavior. Of these, the gas permeability technique is the only method which allows an easy test to determine if diffusion is the rate-controlling mechanism, thus eliminating the uncertainty regarding the limiting transport processes inherent in the other techniques. The two most recent permeability studies are those of Toda10 and Davis." Toda determined the permeability of hydrogen in the a phase of palladium over the temperature range from 170" to 290°C, and over the pressure range from 36 to 630 mm Hg utilizing a steady-state gas-permeability technique. Toda&apos;s result was: J = 1.41 x 10-3 P½ exp(-3220/RT) where J = specific permeability in cc(stp)/sec/cm2/cm, P½ = square root of the inlet pressure in (cm Hg)½, R = Universal gas constant, and T = temperature in deg Kelvin. Davis11 also employed a steady-state gas-permeability technique over the temperature range from 200" to 700°C and over the pressure range from 0.02 to 760 mm Hg. His result for the permeability of hydrogen in the a phase of palladium was: J = 3.15 x 10-3 P½ exp(-A440/RT) In the range of overlapping temperature for these two investigations, the values of the specific permeability calculated from the above two equations differ by a factor of about 1.8. In the present investigation, the permeation of hydrogen in the a phase of palladium was determined over a wide temperature range, 27" to 436oC, and over the pressure range from 2.9 x 10-5 to 5.0 x 10-3 cm Hg. This temperature range overlaps that of the previous investigations of Toda and Davis, but also covers the lower temperature range which has never before been investigated. The lower pressure range used here avoided the interaction between the dissolved hydrogen atoms observed at higher hydrogen concentrations.&apos; MATERIALS The as-received palladium specimens were cold rolled from a casting and were supplied as 5.08 cm discs of 0.508 and 0.762 mm thickness. According to J. Bishop and Company specifications, the composition of the discs was 99.95 pct Pd, the balance being Cu, Ag, Au, and Ir. In order to obtain samples of varying grain size, the as-received discs were then heat treated. Sample 1 was treated for eight minutes in a nitrogen atmosphere at 810°C and then air-cooled. Sample D was heated first to 550°C in helium. The helium atmosphere was then immediately replaced by hydrogen and the temperature was slowly raised to 1220°C and held for 22 hr. The sample was then cooled to 550°C where the hydrogen was replaced by helium and the disc was further furnace-cooled to room temperature. Sample H was given the same heat treatment, only with hydrogen substituted for helium below 550°C. The reason that hydrogen was not used throughout the entire annealing cycle for samples D and H was to prevent the distortion encountered by low-temperature cycling in hydrogen observed by Darling." After these heat treatments were completed, the

Jan 1, 1970

By T. Y. Yan

SUMMARY Laboratory high pressure column tests have shown that the presence of 1-20 ppm of aluminum ion effectively prevents permeability loss during uranium leaching with leachates containing sodium carbonate. If added after permeability loss has occurred, aluminum ion can restore the permeability to nearly its original value. No deleterious effect was observed on uranium leaching performance and the technique should be quite compatible with all field operations. INTRODUCTION The recovery of uranium values from underground deposits by in situ leaching or solution mining has become economically viable and competitive with conventional open pit or underground mining/milling systems (Merrit, 1971). In situ leaching processes are particularly suitable for small, low-grade deposits located in deep formations and dispersed in many thin layers. Many such ore bodies occur along a broad band of the Gulf Coastal Plain (Eargle et. al., 1971). The advantages of the in situ leaching processes have been reviewed (Anderson and Ritchi, 1968). In the in situ leaching process, a lixiviant containing the leaching chemicals is injected into the subterranean deposit and solubilizes uranium as it traverses the ore body. The pregnant lixiviant or leachate is produced from the production well and is then treated to recover the uranium. The resulting barren solution is made up with the leaching chemical to form lixiviant for re-injection. Upon completion of the leaching operation, the formation is contaminated with leaching chemicals and other species made soluble in the leaching operation and has to be treated to reduce the concentration of these contaminants in the ground water to levels acceptable to the regulatory agencies (Witlington and Taylor, 1978). Restoration is accomplished by injecting a restoration fluid, which could be the fresh water or water containing chemicals, into the formation. As it traverses the leached formation, the restoration fluid picks up the contaminants and is then produced at the production well. This produced water is either disposed or purified for recycle. In both phases of operation, formation permeability or well injectivity is one of the most important parameters which determines the viability of the in situ leaching process. Low formation permeability limits production rates, leading to uneconomical operations. The formation is said to be sensitive if there is a sharp loss of permeability on contact with water and other fluids. Many uranium bearing formations, for example, the Catahoula formation of the Texas Coastal Plain, contain significant amounts of clay minerals which are water sensitive. Serious permeability losses can occur when the pH and chemical composition of the lixiviant is significantly different from that of the formation water. Jones has investigated the influence of chemical composition of water on clay blocking of permeability (Jones, 1964) and Mungan studied permeability reduction through changes in pH and salinity of the water (Mungan, 1965). Various mechanisms of permeability damage have been proposed and reviewed (Jones, 1964; Mungan, 1965; Gray and Rex, 1966; and Veley, 1969). When large amounts of swelling clays are present, a significant fraction of the flow channels in the formation can be reduced due to swelling. However, in most cases, swelling need not be the main cause of permeability losses. Particle dispersion and migration or clay sliming can be more important causes for formation damage. Clay particles entrained in the moving fluids are carried downstream until they lodge in pore constrictions. As a result, microscopic filter cakes are formed by these obstructions, plugging the pores, effectively restricting fluid flow and reducing the formation permeability. Moore found that as little as 1-4 percent clays present in a fine grained sandstone could completely plug the formation if they are contacted by incompatible injected fluids (Moore, 1960). It has been found that injection of NaHC03/Na2CO3 lixiviant into formations with significant clay content often leads to loss of formation permeability and well injectivity. To alleviate this problem a change of the lixiviant composition to KHC03/K2CO3 has been proposed. At present, however, many in situ leaching operations employ NH4HC03/(NH4)2C03 mixtures as a source of carbonates. This approach has been successfully used in South Texas by Mobil, Intercontinental Energy, Wyoming Minerals and U.S. Steel, etc. The use of ammonium carbonates solutions, however, contaminates the formation and requires a time-consuming restoration operation. The other approach to reduce the permeability loss is to pretreat the sensitive formation with chemicals which prevent clay dispersion and migration. Such chemicals include hydroxy-aluminum (Reed, 1972 and Coppel et. al., 1973), hydrolyzable zirconium salts (Peters and Stout, 1977), hydrolyzable metal ions in general (Veley, 1969) and polyelectrolyte polymers (Anonymous). Still another approach, is to minimize the "shock" caused by sudden injection by gradually changing the chemical composition of the injected fluids from that of the formation water. THE APPROACH Since permeability loss can be an important factor limiting the efficiency and economic viability of the in situ leaching process, a study was initiated on

Jan 1, 1982

By H. E. Cline, J. L. Walter

Grain boundary sliding and migration were studied in pure aluminum bicrystal and polycrystal samples with two-dimensional grain structure. Scratches, 50 P apart, were used for measurement of sliding and migration distanceso. Samples were deformed at constant rate at 315C and events recorded continuously on wrotion picture film. Electron micrograPhs of boundary-scratch intersections were obtained. Yield and flow stress values were measured. The sequence of sliding and migration events for a three-grain junction is described in detail. Sliding depended only on the resolved shear stress imparted to the boundary. Sliding was accowmodated by formation of shear zones in grains opposite triple points and adjacent to curved boundaries. These shear zones provided the driving force for grain boundary migration. Migration caused rumpling of the boundaries, decreasing the sliding rate. Sliding and migration generally began at the same time, occurred simultaneously and ended at the same time. In the bicrystal, sliding and migration rates were proportional. Initial sliding rules of 5 X joe cm per sec. were measured for the polycrystal and bicrystal samples. These sliding rates agree wilh the internal friction experirnents of K;. The observations seem consistent with a viscous boundary sliding nzechanism. GRAIN boundary sliding is the translation of one grain relative to its neighbor by a shear motion along their common boundary. Sliding is thought to be an important mode of deformation at elevated temperatures and at low strain rates such as prevail in creep,&apos; and perhaps in the area of superplastic behavior.2"4 Although much work has been done to investigate grain boundary sliding, the effort has not led to the identification of a mehanism. KG showed that grain boundaries in aluminum exhibit a viscous nature under very small displacements of internal friction measrements. Various dislocation mechanisms have been proposed but are without conclusive experimental support. Attempts to relate sliding to 6&apos;s viscous boundaries have been unsuccessful in that measured rates of sliding are always several orders of magnitude lower than KG&apos;S results would predict.= In bi crystals7and polycrystalsR of aluminum tested under constant load, the grain boundary sliding was found to be proportional to the total creep elongation which indicated that sliding might be controlled by deformation of the grains. Shear zones were observed to extend beyond grain boundaries at triple points to accommodate the sliding.8 Surface observations brought forth the opinion that sliding and migration occurred alternately, in sequence.&apos; Measurements of sliding at the surface have been criticized because they might not be representative of the interior of the sample. Generally speaking, it seemed that much of the previous work and knowledge was based on observations made at relatively low magnification and examination of samples after deformation had been accomplished. Thus, it was the purpose of the present study to continuously record, at high magnification, the events occurring during the deformation of pure aluminum. Samples with two-dimensional grain structures were used to simplify interpretation of the results. The sliding and migration of small areas of many samples were continuously recorded by time-lapse motion pictures. Replicas of the surface were used to provide high-resolution electron micrographs. These observations, coupled with tmsile strength data, provide sufficient information to arrive at an understanding of the phenomenon. EXPERIMENTAL PROCEDURE An ingot of 99.999 pct A1 was rolled to sheet, 0.127-cm thick. Tensile specimens, with a gage length of 0.85 cm, were machined from the sheet. Bicrystal tensile specimens, of the same dimensions, were spark cut from a large bicrystal ingot. The grain boundary was oriented at 45 deg to the tensile axis. The surfaces of the tensile samples were ground flat on fine metallographic paper and were then electropolished in a solution of 75 parts absolute alcohol and 25 parts of perchloric acid. The solution was cooled in an ice-water bath. Using a weighted sewing needle suspended from a small pivot on a precision milling machine, a grid of fine scratches, 50 p apart, was scribed on one surface of the sample. The polycrystalline samples were then annealed in hydrogen for 15 min at 350" to 400°C to produce a two-dimensional grain structure of about 0.2-cm average grain diameter which would not undergo further growth at the test temperature, 315OC. Examination of both surfaces of the samples showed that the grain boundaries were perpendicular to the surface of the polycrystal and bicrystal samples. A hot-stage tensile machine was constructed for use with an optical microscope as shown in Fig. 1. The specimen is shown mounted in the grips. The grips ride in V-ways so that the sample can be mounted without damage. The rear grip is free to slide so that when the sample expands during heating it is not put under a compressive stress. When the grips and samples are at temperature, the rear grip is locked in place by two set-screws. The other grip is connected to a synchronous drive motor which, through a worm gear and a fine-threaded rod, deforms the

Jan 1, 1969

By W. C. Clarke

An empirical study of the nature of the embrittle-ment which occurs in martensitic and semiaustenitic precipitation hardening stainless steels upon exposure at temperatures of from about 550" to 875°F has been undertaken. This work was aimed at determining cazusation and means of controlling this phenomenon. A commercial copper bearing precipitation hardening alloy was used as a basic material for study. The effect of heat treatment variables was studied as was the effect of variations in analysis. It is concluded from the evidence that martensitic and semiaustenitic precipitation hardening stainless steels are subject to 885°F ernbrittlement similar to that observed in the straight chromium stainless steels. A characteristic of precipitation hardening stainless steels which has limited their use in certain applications is that they embrittle when held at temperatures in the range of from about 550" to 900°F. This is true to a more or less degree in all currently available alloys, either the basically martensitic type or the semiaustenitic type. The rate of embrittlement varies markedly with exposure temperature, being low at 550" to 600°F and in-creasing as the temperature increases. In spite of this embrittlement, these alloys with their unique combination of high mechanical strength, reasonable toughness, and good corrosion resistance are used in many hundreds of applications. Nevertheless, there are potential applications where the embrittle-ment described is a limiting factor. The purpose of this investigation was to study the embrittlement of these alloys and to find a way to control or eliminate it. GUIDELINES USED IN PRESENT WORK The work reported in this paper is based on a study of 17-4 PH*, a very widely used alloy. It has been used *Trademark of Armco Steel Corp., licensor. in pressurized water and boiling water atomic reactors operating at about 550°F for a number of years. As the life of such equipment is extended or operating temperatures are raised, the possibility of embrit-tlement becomes of increasing concern to materials engineers. Much investigation work was done with respect to the use of 17-4 PH at 550°F. K. C. Antony&apos; states "Such estimation" (of an activation energy for the diffusion of chromium in iron) "would indicate W. C. CLARKE, Jr. is Senior Research Engineer, Advanced Materials Division, Armco Steel Corp., Baltimore. Md. This manuscript is based on a talk presented at the symposium on New Developments in Stainless Steel, sponsored by the IMD Corrosion Resistant Metals Committee, Detroit, Mich., October 14-15, 1968. significant secondary aging is improbable at temperatures less than 700°F within normal component service life". This statement is modified however by the recognition of the accelerating tendencies of applied stress and internal stress as well as the possible effect of irradiation. In this investigation of 17-4 PH, the H 1100 (1900°F-1 hr oil quench or air cool + 1100°F-4 hr-air cool) condition was used, partly because this condition is normally used in atomic reactors. As shown later, the precipitation hardening temperature has no real bearing on the rate of embrittlement. An exposure temperature of 800°F was selected since embrittlement at 800°F is rapid, permitting development of relative data in time periods of 400 to 500 hr. For those not familiar, a nominal present day analysis of 17-4 PH is: C Mn P S SiCrNiCuCbN 0.04 0.30 0.015 0.015 0.60 16.00 4.30 3.25 0.23 0.030 TYPICAL BEHAVIOR OF 17-4 PH Figs. 1 and 2 show the behavior of a commercial heat of 17-4 PH under the conditions defined. Characteristically, 800°F exposure causes a rapid drop in Charpy V-notch impact strength. Tensile and yield strengths gradually increase and a gradual loss of elongation and reduction of area occur, accompanied by an increase in hardness. Notched tensile strength increases to 125 hr exposure and then sharply decreases after exposure for 500 hr. The notched vs un-notched tensile ratio remains virtually constant to exposure for 125 hr (1.67 to 1.56) but drops to 1.15 after 500 hr. Tensile ductility is not alarmingly affected even after much longer exposure times than these. For example, samples aged at 1100°F for 1 hr exposed at 800°F for 4000 hr showed a drop in elonga-tion of from 13 to 11 pct and in reduction of area of from 58 to 37 pct. Notched impact is the property SmIgth KSI 3JJ[/__________^UTS-Nrteh 260 ;/- 240 —^ 200 UTS-Smooth________._, o ioo mo Sob" m Too Hours Exposure Fig. 1—Effect of exposure at 800°F for various times on notched tensile strength and smooth tensile and 0.2 pct yield strength of 17-4 PH in the H 1100 condition.

Jan 1, 1970

By R. E. Powers, E. H. Kinelski, H. A. Morrissey

A group of 17 American blast-furnace sinters, an American open-hearth sinter, an American iron ore, and a Swedish sinter were used to evaluate testing methods adapted to appraise sinter properties. Statistical calculations were performed on the data to determine correlation coefficients for several sets of sinter properties. Properties of strength and dusting were related to total porosity, slag ratio, and total slag. Reducibility was related to the degree of oxidation of the sinters. THIS report to the American iron and steel industry marks the completion of a 1949 survey of blast-furnace sinter practice sponsored by the Subcommittee on Agglomeration of Fines of the American Iron & Steel Institute. The use of sinter in blast furnaces, sinter properties, raw materials, and sinter plant operation have been reported recently.1,2 After preliminary research and study," test procedures were adapted to appraise the physical and chemical properties of sinter to determine what constitutes a good sinter. During the 1949 to 1950 plant survey each plant submitted a 400-lb grab sample to research personnel at Mellon Institute, Pittsburgh, Pa. A 400-lb sample was also submitted from Sweden. In addition, 2 tons of group 3 fines iron ore were obtained from a Pittsburgh steel plant. The following tests were performed on the iron ore sample and on the 19 sinter samples: chemical analysis; impact test for strength and dusting; reducibility test; surface area measurements, B.E.T. nitrogen adsorption method; S.K. porosity test; Davis tube magnetic analysis; X-ray diffraction analysis for magnetite and hematite; and microstructure. Results of these evaluations are discussed in this paper and supply a critical look at testing procedures used to determine sinter quality. Sinter Tests and Results Each 400-lb grab sample of sinter was secured at a time when it was believed to represent normal production practice at each plant. It was not possible to use the same sampling procedures throughout the survey; consequently samples were taken from blast-furnace bins, cooling tables, and railroad cars. These were very useful for evaluation of test methods, since they were obtained from plants with widely divergent operations. With the exception of Swedish sinter and sinter sample N, which were produced on the Greenawalt type of pans, all survey sinters were produced on the Dwight-Lloyd type of sintering machines. Sinters submitted for test were prepared in identical manner by crushing in a roll crusher (set at 1 in.), mixing, and quartering. To secure specific size fractions for tests, one quarter of the sample was crushed in a jaw crusher and hammer mill to obtain a —10 mesh size. The remainder was screened to obtain specific size fractions. The group 3 fines iron ore was dried and screened and samples were taken from selected screen sizes to be used for various tests. Prior to testing, each ore sample except the —100 mesh fraction was washed with water to remove all fine material and was then dried. This iron ore, a hematitic ore from the Lake Superior region, was used as a base line for comparing results of tests on sinters. The iron ore did not lend itself to impact testing, since it was compacted rather than crushed in the test, and no impact tests are reported. However, the iron ore was subjected to all remaining physical tests to be described. Chemical Analysis: Table I presents chemical analyses performed on the survey sinter samples. Included in this table are data obtained from determination of FeO and the slag relationships: CaO + MgO and total slag (CaO + MgO + SiO, SiO2 + Al2o3 + TiO2). The percentage of FeO was used as an indication of the percentage of magnetite in the sinter. It was believed that slag relationships could be correlated with sinter properties. During initial determination of FeO great disagreement arose among various laboratories, both as to the results and the methods of determining values. Table I lists the values of FeO resulting from the U. S. Steel Corp. method of chemical analysis,&apos; which reports the total FeO soluble in hydrochloric and hydrofluoric acids (metallic iron not removed) with dry ice used to produce the protective atmosphere during digestion. Use of dry ice was a modification required to obtain reproducible results. In this method, the iron silicates and metallic iron are believed to go into solution and are therefore reported as FeO. This is important, for in the study of the microstructure of sinters, glassy constituents suspected of containing FeO as well as crystallized phases of undetermined identity which may also contain FeO have been observed. Strength Test by Impact: In evaluating sinter quality, one of the properties stressed most by blastfurnace operators is strength. This strength may be described as the resistance to breakage during handling of sinter between the sinter plant and the blast-furnace bins. It is also the strength necessary to withstand the burden in the blast-furnace. After

Jan 1, 1955

By J. W. Spretnak, D. A. Chatfield, G. W. Powell, J. R. Eifert

In nzost cases, the driving force for a lattice transformation is produced by supercooling below the equilibriunz transformation temperature. The interfnce reaction in isothermally annealed, multiphase diffusion couples may involve a luttice transformation which also requires a driving force. Direct experinzental evidence has been obtained for the existence of the driring force in the form of a supersaturated phase at the aocc)-0@cc) interface in Cu:Cu-12.5 ult pct A1 couples; the super saturation is equivalent to an excess free energy of approximately 3 cal per mol at 905. A tentatiue interpretation of the dynanzic situation a1 the interface based on the free energy-composition diagram is proposed. THE presently accepted theory of diffusion in multiphase couples1 states that there will be a phase layer in the diffusion zone for every region which has three degrees of freedom and which is crossed by the diffusion path in the equilibrium phase diagram. For binary systems, this restriction excludes all but single-phase fields and, for ternary systems, only one- and two-phase fields are included. In addition, Rhines"~ as well as other investigators3 6 have reported that the compositions of the various phases adjacent to the interfaces are, for all practical purposes, the compositions given by the intersections of the diffusion path with the solubility limits of the single-phase fields of the equilibrium phase diagram. Some studies of the rate of thickening of these intermediate diffusion layers indicate that the thickness of the layer changes para-bolically with time, or: where x is the position of the interface relative to an origin xo, t is the diffusion time, and k is a temperature-dependent factor. crank7 shows mathematically that, if the compositions at an interface are independent of time and the motion of the interface is controlled by the diffusion of the elements to and from the interface, then the segments of the concentration penetration curve for a semi-infinite step-function couple will be described by an equation of the form: hence, Eq. [l] follows from Eq. (21 if the interface compositions are fixed and if the motion of the interface is diffusion-controlled. Although the concept of local equilibrium being attained at interfaces has assumed a prominent role in the theory of diffusion in multiphase couples, experimental evidence and theoretical discussions which challenge the general validity of this concept have been reported in the literature. arkeen&apos; has stated that strict obedience to the conditions set by the equilibrium phase diagram cannot be expected in any system in which diffusion is occurring because diffusion takes place only in the presence of an activity gradient. Darken also noted that it is usually assumed that equilibrium is attained locally at the interface although the system as a whole is not at equilibrium, the implication being that the transformation at the interface is rapid in comparison with the rate of supply of the elements by diffusion. ISirkaldy3 indicates agreement with Darken in that he believes the concept of local equilibrium is at best an approximation because the motion of the phase boundary requires that there be a free-energy difference and, hence, a departure from the equilibrium composition at the interface. Seebold and Birks9 have stated that diffusion couples cannot be in true equilibrium, but the results obtained are often in good agreement with the phase diagram. The initial deviation from equilibrium in a diffusion couple will be quite large because alloys of significantly different compositions are usually joined together. Kirkaldy feels that the transition time for the attainment of constant interface compositions (essentially the equilibrium values) will be small, although in some cases finite. Castleman and sieglelo observed such transition times in multiphase A1-Ni couples, but at low annealing temperatures these times were quite long. Similarly, ~asing" found departures, which persisted for more than 20 hr, at phase interfaces in Au-Ni and Fe-Mo diffusion couples. Braun and Powell&apos;s12 measurements of the solubility limits of the intermediate phases in the Au-In system as determined by microprobe analysis of diffusion couples do not agree with the limits reported by Hiscocks and Hume-Rothery13 who used equilibrated samples. Finally, Borovskii and ~archukova&apos;~ have stated that the determination of the solubility limits of phase diagrams using high-resolution micro-analyzer measurements at the interfaces of multiphase couples is not an accurate technique because of deviations from the equilibrium compositions at a moving interface; diffusion couples may be used to map out the phase boundaries in the equilibrium diagram, but the final determination of the solubility iimits should be made with equilibrated samples. The purpose of this work was to investigate the conditions prevailing at an interface in a multiphase diffusion couple and to compare the interface compositions with those associated with true thermodynamic equilibrium between the two phases. Microanalyzer techniques were used to measure interface compositions in two-phase Cu-A1 diffusion couples annealed at 80@, 905", and 1000°C for various times.

Jan 1, 1969

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young&apos;s modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young&apos;s modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman&apos; noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig&apos; observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity&apos; or the paramagnetic susceptibility.&apos; Likewise, no one has noted a change in crystal symmetry. In the present investigation Young&apos;s modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,&apos; and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.&apos; The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder&apos; the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young&apos;s Modulus: For measurement of Young&apos;s modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young&apos;s modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young&apos;s modulus at 25°C, Fig. la, is 28.2~10" dynes per cm&apos; (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;&apos; the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By W. M. Robertson

The formation of grain boundary grooves on surfaces of poly crystalline samples of cobalt and iron immersed in liquid lead has been studied. The grooves form by volume diffusion of the solutes cobalt and iron in the liquid. The diffusion coefficients of the solutes in liquid lead are derived from the measured rate of grooving. The diffusion coefficients are described by the relation D = Do exp (-Q/RT), with, for cobalt, Do = 4.6 x 10-4 sq cm per sec and Q = 5300 ± 800 cal per mole, and for iron, DO = 4.9 x 10-3 sq cm per sec and Q = 10,500 ± 1500 cal per mole. LIQUID metal-solid metal interactions occur at solid-liquid interfaces. Interfacial energy provides a driving force to change the morphology of the interface. Mullins1,2 has derived expressions for the kinetics of interface morphology changes driven by capillarity. These expressions can be applied to an isothermal system of a solid in equilibrium with a liquid saturated with the solid. Surface profile changes can occur by volume diffusion of the solute in the liquid, by volume self-diffusion in the solid, and by interfacial diffusion at the liquid-solid interface. A groove will form at the intersection of a grain boundary with a solid-liquid interface, reducing the total interfacial free energy of the system. The solid-liquid interfacial energy ? must be greater than half the grain boundary energy of the solid ?6 for Mullins&apos; calculations to apply. If ? is less than ?b/2, then the liquid penetrates the boundaries, separating the grains rather than forming grooves. Boundary penetration did not occur in the work described here. where CO is the equilibrium volume concentration of the solid in the liquid, Dv the volume diffusion coefficient of the solid in the liquid, ? the interfacial free energy of the solid-liquid interface, O the atomic volume of the solid crystal, k Boltzmann&apos;s constant and T the absolute temperature. Eqs. [1] and [2 ] also apply to grooving by volume self-diffusion in the solid,1 with CoODv = D Self, where DSelf is the volume self-diffusion coefficient of the solid. For a grooving mechanism of interfacial diffusion at the solid-liquid interface, the groove width is given by2 where CS is the interfacial concentration of the diffusing species, and DS is the interfacial diffusion coefficient. Eqs. [1] and [3] can be used to determine the mechanism of groove growth. A t1/3 dependence of the growth indicates volume diffusion and t1/4 indicates interfacial diffusion. In some cases, volume diffusion and interfacial diffusion both can contribute substantially to the grooving process, causing the time dependence to be intermediate between t 1/3 and t1/4.3 For these cases, the relative contributions of the two processes can be separated.4 However, in many cases, one process will be dominant, and the data can be analyzed on the basis of Eq. [1] or Eq. [3] alone. The time dependences for volume diffusion in a liquid and volume self-diffusion in a solid are the same. However, the self-diffusion contribution of the solid is usually negligible compared to volume diffusion in the liquid. After the grooving mechanism has been determined, Eq. [1] or Eq. [3 ] yields the kinetic parameter A or B. The kinetic parameter can be used to calculate values for the unknown quantities in the product CD?. Usually C is known or can be estimated. If ? is known, then D can be calculated. In a measurement of grain boundary grooving of copper in liquid lead,&apos; the time dependence indicated volume diffusion in the liquid. The quantities Co, Dv, and ? were obtained from the literature, giving excellent agreement between the observed values of A and the values calculated from Eq. [2 ].5 In a study of the grooving of several refractory metals in liquid tin and liquid silver, A1len6 educed that grooves formed by volume diffusion in the liquid. In a study of nickel in a nickel sulfide melt, Steidel, Li, and spencer7 found volume diffusion grooving kinetics. Both Dv and ? were unknown, so they could not obtain either one separately, though they did obtain a reasonable value for the temperature dependence of the product Dv ?. Several methods have been used to obtain surface profiles. It can be done by sectioning through the interface7 or by chemically removing the liquid from the solid surface after solidification of the liquid.6 However, if the liquid dewets the solid on removing the solid from the melt, then the interface can be observed directly. This method was used previously&apos; and was utilized also in the present study. EXPERIMENTAL PROCEDURE Lead of 99.999 pct purity was obtained from American Smelting and Refining Co. Cobalt sheet was obtained from Sherritt-Gordon Mines, Ltd., with a nominal purity of 99.9 pct, the principal impurities being nickel, iron, copper, carbon, and sulfur. The sheet was

Jan 1, 1969

By M. C. Fuerstenau, D. W. Fuerstenau

Studies of the collection of alkali and ammonium halides utilizing vacuum flotation techniques and contact angle measurements show that ionic size controls the flotation of techniquesthese halides with amine salts measurementsas collector. Contact angles of air bubbles on sylvite in saturated brines were withaminemeasured salts asascollector.a function of such variables as collector addition, length of collector chain, and pH of the brine. No contact occurs between halite and an air bubble in brines containing dodecylammonium acetate as collector. LONG-CHAINED aliphatic amine salts have been used for the separation of sylvite (KCl) from halite (NaCl) by flotation.1,2 It is puzzling how these two minerals, which are so similar chemically and crystallographically, can be separated by this method. Gaudin" has postulated that the difference in floatability of halite and sylvite with salts of primary amines depends on ionic size: In the case of amine flotation, the cation would attach itself to the chloride. I have a speculation there, which I cannot prove, that the ammonium group, that is the —NH3 group in the amine, floats potassium chloride because the dimensions of this grour, as it has been measured in other compounds is almost identically the dimensions of the potassium ion, quite different from the sodium ion, and so it fits where potassium had been, in place of it and not attached to it. Apparently, because an aminium ion (RNH3+) is much larger than a sodium ion, it cannot fit into the lattice of halite. Taggart also has speculated that ionic size may control the floatability of sylvite.4 The object of this experimental investigation has been to test this hypothesis and to study what controls the adsorption of cationic collectors at the surface of sylvite. Since collection is to be approached from the viewpoint of ionic size, the ionic radii that are of interest in this work are presented in Table I. The values of the ionic radii of the ions listed in Table I, except NH4+, are those given by Pauling." Several different values for the radius of the ammonium ion have been given, but that of Goldschmidt6 seems to be preferred. The radius of the charged head of a dodecylammonium ion is assumed to be the same as that for the ammonium ion. Little experimental work has been reported in the technical literature concerning the separation of sylvite from halite by flotation. Guyer and Perren studied the separation by flotation of 50 pct binary mixtures of NaCl, KC1, NH,Cl, NaNO3, KNO3, K2SO4, and Na,SO, using either oleic acid or a sodium sul-fonate as collector.&apos; It is possible to measure floatability under actual flotation conditions where all three phases, air- water-mineral, are present by vacuum flotation tests and contact angle measurements.9 Both of these techniques were used in the experimental approach in this paper. Experimental Method and Materials The vacuum flotation tests were run with glass-stoppered pyrex graduated cylinders. Twenty-five ml graduates were used to test the floatability of all salts studied except rubidium and cesium salts. For each test distilled water containing the desired collector concentration was saturated with the salt to be floated. Sufficient salt (—48 mesh) was added to leave about 2 ml of solids in the bottom of the graduate. After the graduate had been agitated several minutes to saturate the solution with air, a vacuum was applied. If the salt were floatable in the collector solution, the gas bubbles attached themselves to the particles, and the particles floated to the surface. In determining the floatability of the expensive Rb and Cs halides, the experiments were run in 10 ml graduates with about 11/2 ml of collector solution initially. Contact angles were measured in the usual manner except that the solutions had to be previously saturated with the mineral to avoid dissolution of the crystal. Solutions for studying contact angles were made by adding the desired amount of collector to a saturated brine, giving the collector concentration in molarity. The mixture was agitated until dissolution of the collector was complete, with the exception of those concentrations greater than about millimolar. At these high concentrations complete dissolution of the collector was impossible. The face of the mineral to be tested was a freshly cleaved crystal of halite or sylvite. The mineral was placed in the brine and conditioned with collector for at least 15 min, which was found to be long enough to obtain a maximum value for the contact angle. The temperature remained constant during each experiment. The experiments were run at 24°C ±2°C. For contact angle measurements, a crystal of halite from Carlsbad, N. M., was used. Several samples of sylvite were used in this work: a crystal of sylvite from Stassfurt, Germany; a crystal from Carlsbad, N. M.; and a crystal of chemically pure potassium chloride. Saturated brines were made from reagent grade chemicals and distilled water.

Jan 1, 1957

By H. Conrad, V. V. Damiano, G. J. London

A method is described for producing single crystals of high-purity beryllium, Be-4.37pct Cu, and Be-5.24 pct Ni. These crystals were prepared for testing in compression parallel to the [0001] by orienting and lapping to within ±3&apos; of arc of the (0001). Microstrain testing apparatus is described along with c axis compression results for ingot purity beryllium, twelve-zone-pass material, and the above-mentioned alloys. Results show no measurable plasticity for the ingot purity material from -196" to 400°C, although some surface traces of (1122) slip was observed at 200°C and above. The twelve-zone-pass material shows substantial microstrain plasticity at 220°C with slip on (1122). Both alloys show significant plasticity at room temperature and above with slip also on (1122) planes. THE two slip systems which normally operate during the plastic deformation of beryllium in the vicinity of room temperature are:&apos; basal slip (0001)(1120) and prism slip . Pyramidal slip with a vector inclined to the basal plane has been reported for elevated temperatures,&apos;-a but occurs near room temperature only at very high stresses.~ A summary of the available data on the effect of temperature on the critical resolved shear stress for slip on these systems has been compiled by Conrad and Perlmutter.~ It has been postulated6&apos;7 that one of the principal factors contributing to the brittleness of poly crystalline beryllium at temperatures below about 200°C is the difficulty of operating pyramidal slip with a vector inclined to the basal plane. Hence, detailed information on the operation of such a slip system is important to understanding the brittleness of beryllium. The operation of pyramidal slip with a vector inclined to the basal plane is best accomplished in beryllium by compressing single crystals in a direction parallel to the c axis. In such a test the resolved macroscopic shear strzss on the basal and prism planes is zero and (1012) twinning which is favored by tension along the c axis does not occur. Hence, in c axis compression of beryllium the normal deformation modes are inhibited and the operation of pyramidal slip with a vector inclined to the basal plane is favored. In the present investigation, c axis compression tests were performed on beryllium single crystal as a function of temperature (77" to 700°K), purity (commercial and twelve zone pass), and alloy content (4.37 wt pct Cu and 5.24 wt pct Ni). Presented here is a description of the test techniques employed and the gross mechanical behavior observed. A detailed analysis of the slip traces developed on the surfaces of the deformed specimens during these tests and the results of electron transmission studies of the deformed crystals are given in a separate paper.B PROCEDURE 1) Materials and Preparation. Single crystals about 1 in. diam were prepared of the following materials: commercial-purity beryllium, high-purity beryllium, and two beryllium alloys, one with 4.37 wt pct Cu and the other with 5.24 wt pct Ni. The commercial-purity single crystals were obtained by cutting specimens from large-grained ingot of Pechiney SR material, which is approximately 99.98 pct pure. The high-purity crystals were prepared by floating-zone refining (twelve passes) a rod (7 in. by 1 in, diam) of Pechiney SR grade cast and extruded beryllium. Although an absolute chemical analysis of the zone-refined material was not established, mass spectro-graphic analysis, emission spectrographic analysis, and y activation analysis indicated that it contained in atomic fractions about 5 to 10 ppm each of carbon and oxygen, 1 to 5 ppm each of nickel and iron, and about 1 to 2 ppm of copper, with the remaining residual impurities being less than 1 ppm. Further indication of the purity of this material is provided by the critical resolved shear stress for basal slip, which was approximately 300 psi. The starting material for the alloy single crystals was 1-in.-diam floating-zone-refined (six passes) rod of Pechiney SR grade beryllium. Two such rods were wrapped respectively with sufficient weight of wire of high-purity copper (99.999 pct) or nickel (99.999 pct) to yield a 5 wt pct alloy. A seventh floating-zone pass was then applied to each of the rods to accomplish the initial alloying and an eighth pass for homogenization. Analytical samples were taken from regions of the rod immediately adjacent to where the mechanical test specimens were cut; these indicated 4.37 wt pct Cu and 5.24 wt pct Ni. 2) Crystal Orientation. To avoid the occurrence of basal slip during c axis compression testing, it is necessary to load the crystals as nearly parallel to the c axis as possible. Preliminary c axis compression tests indicated that plastic flow and/or fracture occurred at stresses of the order of 300,000 psi; hence on the basis of a critical resolved shear stress for basal slip of 300 to 400 psi, the maximum crystal misorientation permitted is about 4 to 5&apos; of arc. Since this accuracy cannot be obtained using the usual back-

Jan 1, 1969

By Leo F. Reinartz

It was with humility that I accepted the invitation of the Board of Directors of our Institute to deliver the Twentieth Howe Memorial Lecture. Many previous lecturers could speak from personal experience of the great work done by Professor Howe. It was not my privilege to be one of his students but, indirectly, I came under the influence of his work many years ago. My mentor in Metallurgy at Carnegie Institute of Technology, Prof. Fred Crab tree, was an ardent admirer of Professor Howe and his work. Professor Crabtree taught me early to appreciate Professor Howe&apos;s love of truth and keen desire to find a scientific reason for every metallurgical phenomenon. In this early search, Professor Howe encountered many unexplainable facts. Nevertheless, in the classic text, "The Metallurgy of Steel," published in 1891, he indicated that he believed Research could light the way. Under the heading of "The Treachery of Steel" he said: "In the early use of Bessemer and Open Hearth Steel, many then unexplained and hence mysterious failures occurred. With our present knowledge, an easy explanation of most of them would probably have been seen. But even today certain unexplained and apparently inexpli- cable failures occur in steel; inexplicable in spite of full and intelligent investigation." Then Professor Howe continued to talk about "the trustworthiness of steel" in the following manner: First, the steel-maker has learned by experience. He knows today far better the effects of a high percentage of carbon or of phosphorus; of cracks, pipes and blow-holes; of segregation and imperfect mixing; of over-heating; of finishing too hot or too cold. Knowing, he guards against them more effectually, and keeps at home much steel that he would formerly have sent into the market. Those who would not, or could not learn and do, have been driven out of the business; the conditions necessary for producing good sound steel by the acid Bessemer and the acid Open Hearth processes have been mastered. By and by, the basic process came along with new conditions, new liabilities to unsoundness, a great hue and cry about mysterious fractures followed, and Lloyd&apos;s register provisionally forbade the use of basic steel. Much basic steel was irregular and brittle throughout; too much carbon, too much phosphorus, too cold teemings—imperfect mixing. Still there was little doubt that, with further experience, these difficulties of the basic process would be mastered as those of the acid process had been. This shows that Professor Howe could not take anything for granted. Believing that careful research would find the answer to all mysterious phenomena, he was several generations ahead of the practical acceptance and adoption of this principle.

Jan 1, 1943

By Leo F. Reinartz

It was with humility that I accepted the invitation of the Board of Directors of our Institute to deliver the Twentieth Howe Memorial Lecture. Many previous lecturers could speak from personal experience of the great work done by Professor Howe. It was not my privilege to be one of his students but, indirectly, I came under the influence of his work many years ago. My mentor in Metallurgy at Carnegie Institute of Technology, Prof. Fred Crab tree, was an ardent admirer of Professor Howe and his work. Professor Crabtree taught me early to appreciate Professor Howe&apos;s love of truth and keen desire to find a scientific reason for every metallurgical phenomenon. In this early search, Professor Howe encountered many unexplainable facts. Nevertheless, in the classic text, "The Metallurgy of Steel," published in 1891, he indicated that he believed Research could light the way. Under the heading of "The Treachery of Steel" he said: "In the early use of Bessemer and Open Hearth Steel, many then unexplained and hence mysterious failures occurred. With our present knowledge, an easy explanation of most of them would probably have been seen. But even today certain unexplained and apparently inexpli- cable failures occur in steel; inexplicable in spite of full and intelligent investigation." Then Professor Howe continued to talk about "the trustworthiness of steel" in the following manner: First, the steel-maker has learned by experience. He knows today far better the effects of a high percentage of carbon or of phosphorus; of cracks, pipes and blow-holes; of segregation and imperfect mixing; of over-heating; of finishing too hot or too cold. Knowing, he guards against them more effectually, and keeps at home much steel that he would formerly have sent into the market. Those who would not, or could not learn and do, have been driven out of the business; the conditions necessary for producing good sound steel by the acid Bessemer and the acid Open Hearth processes have been mastered. By and by, the basic process came along with new conditions, new liabilities to unsoundness, a great hue and cry about mysterious fractures followed, and Lloyd&apos;s register provisionally forbade the use of basic steel. Much basic steel was irregular and brittle throughout; too much carbon, too much phosphorus, too cold teemings—imperfect mixing. Still there was little doubt that, with further experience, these difficulties of the basic process would be mastered as those of the acid process had been. This shows that Professor Howe could not take anything for granted. Believing that careful research would find the answer to all mysterious phenomena, he was several generations ahead of the practical acceptance and adoption of this principle.

Jan 1, 1943

By R. J. Colony

DEPOSITS of iron are widely scattered in the folded Cretaceous rocks and the associated igneous intrusives of Puerto Rico. Most of them are too small for commercial development, but a few have aroused some scientific and economic interest, among them the large body of residua] limonite at the west end of the island near Mayaguez1-6 (Fig. 1) and the mixed hematite and magnetite deposit on the southern slopes of the Sierra de Cayey, about four miles north of Arroyo.7-9 Neither of these orebodies has been developed, nor have investigations of the widely distributed deposits of magnetite, which include all the remaining occurrences of iron deserving of economic consideration, proceeded beyond the exploratory stage. With the possible exception of the mixed deposit near Arroyo, the magnetite is directly associated with andesitic and dioritic intrusives, which invade the Cretaceous rock section, and the bulk of it, occurring in calcareous sediments, is clearly of contact-replacement origin. The small deposit on Rio Portugues, north of Ponce, is found in a limestone band near its contact with an andesite dike.10,11 Two deposits of unde-

Jan 1, 1935

By H. H. Dreissen, F. J. Fontein

The operating principle of the classifying cyclone has been described often but some special aspects of the cyclone receive further clarification here. In addition, several uses of the classifiers are summarized and made clear by means of practical examples. In coal and ore washeries, the washing cyclone is widely used for the separation by specific gravity of sizes up to about 12 mm. This application has lately been extended to the separation by specific gravity of particles up to about 50 mm. This use makes special demands on the construction and wear resistance of the cyclone. The sieve bend, a development of the Dutch State Mines which is less well known than the hydrocy-clone, is dealt with at some length. The sieve bend is an apparatus designed for wet screening. Attention is given to the variables influencing the performance of the sieve bend. Hydrocyclones are now so widely applied that it would be difficult to find an industry not, directly or indirectly, using them or knowing how to use them since publications on this subject abound.1-3,5,9-11,13-15 However, because of the large number of variables influencing the operation of classifying cyclones, it is not entirely possible to calculate the results of this type of cyclone. Therefore, a number of lesser known variables will be discussed here along with some special applications of the classifying cyclone. FACTORS INFLUENCING CYCLONE CLASSIFICATION Shape of Particles: The shape of particles may cause a much coarser classification than the one expected, considering the sieve analysis and the cyclone dimensions chosen. This was clearly shown by feeding a mixture of spheres and disks in water into a cyclone. The spheres were 0.36 mm diam and the disks, 3 mm diam and 0.03 mm thick. These dimensions were chosen in order that the disks and spheres might have the same rates of fall under gravity. Both spheres and disks had a specific gravity of 1.05. The results obtained with these particles in a cyclone are summarized in Table I. Test No. 2 shows that the catch of spheres was

Jan 1, 1963

By Charles Will Wright

The present struggle for economic and industrial supremacy by the Communist world is against the United States, its main target, and the other Free World nations. The basis of industrial power is minerals, so the Communist nations are building up mineral production within their borders, often regardless of costs, and are acquiring quantities of mineral products from Free World countries for future use. They are contracting for additional supplies and advancing funds for the development of these quantities. A number of the less developed mineral producing countries of the Free World are being infiltrated by Communists and Communistic influence. This situation is well known, but as yet little has been done to oppose these activities or to awaken the public to their seriousness. The Communist countries are still far behind the Free World Nations in production of many essential minerals. But, shortages are being made up from Free World nations in exchange for petroleum, manganese ore, chromite and other products. Restrictions on shipments of strategic materials to Communist countries have not been maintained.

Jan 1, 1964