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By Fathi Habashi

CRYSTALLIZATION from aqueous solution is a simple and old method for the recovery of metal values from leach solution. Practically all the methods for the recovery of aluminum from clay are based on the crystallization of an aluminum salt from the leach solution. Differences in solubilities may be used to advantage for separating two metals from the same leach solution. The classical method of Marignac (1866), which makes use of the difference in solubilities of K2TaF7 and K2NbOF5 to separate niobium from tantalum, has been used successfully in the manufacture of these metals (Fig. 10-1). The slurry containing the metal oxides is dissolved in 70 % hydrofluoric acid, diluted, and heated near boiling. A potassium salt is added in sufficient quantity to form the complex fluorides of the niobium and tantalum present. The solution is filtered and allowed to cool. At room temperature most of the tantalum salt crystallizes out while the niobium remains in solution.

Jan 1, 1970

By Laurance L. Oden

The Bureau of Mines is developing melting data for binary combinations of the alkaline earth fluorides and yttria to facilitate the formulation of slag composition. Liquidus and solidus temperatures and solid solubilities were determined for the BaF2-Y203 system, and the information is presented as the phase diagram. The phase diagram was constructed from data obtained by ceramography, X-ray diffraction, and thermal analysis of specimens encapsulated in small molybdenum ampoules. The data indicate a simple eutectic system with maximum terminal solid solubilities of less than 1 mole pct. The eutectic temperature is 1,343° C, and the composition of the eutectic is less than 1 mole pct Y203.

Jan 1, 1970

By Rex O. McLellan

The formation of a monovacancy in a metal is simulated in an elastic model by the displacement of the surface of a small spherical cavity in a large elastic continuum. The application of linear elasticity to this distortion results in a well- known formula for the energy and an expression for the concomitant entropy change due both to the shear strain in the continuum and also to the dilation of the solid resulting from the boundary conditions at the surface of the solid. Elastic data (the sliear modulus and its temperature coelficient) are used to calculate the entropy and energy of formation for many metals. Despite the simplicity of the assumptions involved, the agreement between the calculated entropies and energies and experimental values is remarkably good. In recent years there has been a large increase in measurements of the absolute concentration of mono-vacancies in metals as a function of temperature. Hence new data for both the energy and the noncon-figurational entropy of formation of monovacancies has become available. Recent measurements&apos; of the anomalous (non-Arrhenius) self-diffusion in many bcc metals has also focused interest on the prediction of the thermodynamic parameters of mono- and multi-vacancies in those metals for which no data are available. Damask and Dienes&apos; have discussed the various theoretical calculations of the energy of formation EL, of a monovacancy. These include simple models involving the breaking of atomic bonds on moving atoms from the interior of a crystal to the surface, models combining elastic calculations with surface-energy terms and detailed quantum mechanical calculations. The simler models give the correct order of magnitude of &, but tend to overestimate it by a factor of about two. The quantum mechanical calculations4"7 have been carried out for the noble and alkali metals with generally reasonably good agreement with the available Ef data. The calculation of entropy of formation Sfv14 lnvolves a fundamental calculation of the perturbation of the phonon spectrum caused by the creation of a vacancy. Huntington, Shirn. and wajda8 have given an approximate evaluation of sJV by considering an Einstein model for the localized vibrations in the immediate neighborhood of the defect and then using elastic theory to calculate the entropy associated with the shear stress field in the distorted crystal (as originally proposed by Zenerg). They also included a term due to the dilation of the crystal. They obtained a value of 1.47k for copper, in good agreement with the experimental value (1.50k). However, Nardelli and Tetta- manzi1° have recently shown that neglecting the coupling between atoms (Einstein Model) may lead to a serious error so the agreement may be somewhat fortuitous. In this work simple linear elastic theory is used to calculate the entropy and energy of formation of mono-vacancies. Despite the simplicity of some of the assumptions involved, the agreement with the available experimental data is remarkable. However. the reasonable degree of success in the application of linear elastic calculations to the excess entropy of a solute atom in a dilute solid solution1&apos; indicates that the application of elastic theory to vacancies. where the interaction of different atomic species is not involved, may not be inappropriate. THE ELASTIC MODEL The metal is assumed to be a spherical elastic continuum. A small spherical cavity of volume V = 4i;v:&apos;/3 is cut from the center. removed. and dissolved rever-sibly in the bulk of the material. TO a good approximation no net atomic bonds are broken and the material does not undergo a volume change although the externally measured volume of the body would increase by V. The radius of the sphere of metal is much larger than r Next a negative pressure is applied to the cavity causing its surface to be displaced inward by an amount simulating the relaxation of the lattice around a monovacancy. In this model the energy and entropy accompanying the distortion are taken as 4, and <. As a first approximation the equation of state for the solid is taken as: r = ro(i + *~D LiJ where K is the bulk modulus. P the hydrostatic pressure. Vo the volume of the material at 0°K and zero pressure. and d+/dT = 30. where 0 is the linear thermal expansion coefficient. The variation of entropy with hydrostatic pressure is given by the Maxwell equation: These equations give the entropy change resulting from increasing the hydrostatic pressure from 0 to P as: and since • we have: This is the entropy arising from the dilation resulting

Jan 1, 1970

By Fun-Den Wang

A two-dimensional plane strain analysis by the stiffness matrix method was used to analyze two basic pit slope configurations. The magnitudes and the directions of stresses are given for a V-shape and for a flat-bottom pit with the slope angle varying from 30° to 90° at 10° intervals, Stress effects due to irregular pit configuration or to in-situ forces are discussed. Equations of similitude for gravity loading are given. Expressions are also given for the stresses at the toe as a function of slope angle. Procedures are given for finding the stresses in any geometrically similar pit slope of different dimensions and material properties from the stresses and equations presented in this report. Numerical results show that the V-shape pit slopes have lower stresses than the flat-bottom pit slopes; hence, they are inferred to be more stable.

Jan 1, 1970

Jan 1, 1970

By A. Aly Selim

This report describes the feasibility of predicting percussive drilling rates by equations derived from statistical regression analysis. The least squares statistical method was used and the analysis was performed both by direct and by stepwise linear regression analysis. The predicted penetration rate is a function of the drill power and the physical properties of the rocks penetrated. The results show promise that the technique may be of value in providing a mathematical model by which percussive drill manufacturers and users can predict the performance of a given drill. Experimental work involved two mining type percussive drills. Penetration data for these drills were determined from nine rocks drilled in the laboratory. Drill work rates (power) were determined in a separate series of experiments. Rock physical properties were measured from diamond-drill core samples taken from the same blocks used for percussive drilling.

Jan 1, 1970

By R. K. Iyengar, G. C. Duderstadt

An investigation was carried out to determine the effect of Ca-Si additions on the dissolved oxygen content of liquid steel. An apparent equilibrium was reached after holding the melt for some time when the total oxygen content of the melt was identical with the dissolved oxygen. Results of the investigation show that for deoxidation with silicon and manganese the apparent equilibrium is reached after 8 to 12 min and the oxygen content of the melt is in good agreement with values reported in the literature for similar steel compositions. Ca-Si additions decrease the dissolved oxygen content appreciably below that obtained with Si-Mn deoxidation. It is postulated that some calcium dissolved in liquid steel at the time of its vaporization combines with dissolved oxygen to form CaO which then fluxes the manganese silicate, thereby lowering the activity of the deoxidation products. Slow flotation of calcium silicate inclusions is attributed to their slower growth rate. An addition of aluminum (to yield <0.005 pct Alsol) prior to introduction of Ca-Si improves the kinetics of removal of resulting deoxidation products. WITH the introduction of continuous casting of billets and blooms, application of calcium-containing alloys for deoxidation purposes has gained new interest. More so than in conventional ingot casting, the degree of control of the dissolved and total oxygen contents in steel for continuous casting can determine the success or failure of the operation because these affect both surface (pinholes) and internal quality of the billets. Of the available deoxidizers, only silicon has so far found wide application. However, in the typical range of application (0.20/0.30 pct Si), it is too weak a deoxidizer to suppress pinhole frequency to the level desirable for all but the least demanding appli-cations (approximately 10/50 pinholes per sq ft, de-pending on degree of subsequent reduction). On the other hand, Vincent&apos; has shown that it requires ap-proximately 0.007/0.008 pct A1 soluble in the steel to suppress pinhole formation to <10 pinholes per sq ft. In view of the difficulty of consistently maintaining this aluminum level and the associated problem of tundish nozzle constriction2 when aluminum is added to the ladle, steelmakers have searched for other de-oxidation alloys to circumvent the problem. Calcium-containing alloys offer such a possibility. When employed as a partial substitute for silicon, CaSi (30 pct Ca/60 pct Si) additions are reported to yield adequate pinhole contro1.3 Its use simultaneously preserves the "fluidity" of the steel and ensures good castability.4 Oxygen contents as low as 0.007 to 0.014 pct have been obtained with CaSi additions varying between 3 to 8 lb per ton.5-7 Due to the high degree of vaporization of calcium at the temperature of molten steel and the different methods used to introduce it into the liquid, the reported results show considerable scatter and lack of consistency. According to several investiga- deoxidation tors, the flotation characteristics of CaSi products are not as favorable as those found for alumi-num but are similar to those established for silicates with low alumina content.678 Thus, cleanliness ratings were improved when CaSi was replaced by a com-bination of Si + A1 followed by CaMnSi additions.5,9 In view of the lack of a comprehensive description of the deoxidation potential of CaSi alloys, a study was undertaken of the effect of CaSi additions on oxygen content in comparison to Si + Mn and Si + Mn + Al. The alloy chosen for this study contained 63 pct Si, 32 pct Ca, <3 pct Al, and 2.5 pct Fe. EXPERIMENTAL PROCEDURE The experiments were divided in three groups as shown in Table I. In each group, the CaSi addition was increased successively while maintaining the melt composition constant. The experiments in the third group were designed to determine the effect of prede-oxidation with small amounts of aluminum. Ingot iron, containing 0.02 to 0.03 pct C and 0.03 to 0.05 pct Mn, was melted in a 100-lb magnesia crucible. Pig iron was added to the melt under air in an induction furnace to attain the desired carbon content of 0.05 to 0.15 pct and thereby control the initial oxygen content of the melt between 0.04 and 0.015 pct. After removal of the slag, the furnace was sealed and argon was introduced through an opening in the graphite cover, Fig. 1. When the desired temperature was reached, electrolytic manganese was added to the melt and pin samples were taken (7 mm silica tubing) to establish initial oxygen content. To obtain maximum efficiency, CaSi and metallic silicon were introduced in a sealed steel pipe into the bath. This procedure assured minimum loss of calcium through vaporization as the deoxidants were always released at the bottom of the melt. Samples were taken at regular intervals and quenched in water. Temperature of the bath was measured with a Pt/Pt-10 pct Rh thermocouple. Portions of the pin sample were used for oxygen analysis; five determinations per sample were made to obtain average oxygen content. Oxygen analyses were made by the inert carrier gas fusion method with frequent cross checks with the vacuum fusion method.

Jan 1, 1970

By John F. Abel

At the spring meeting of the Open Pit Division of AIME&apos;s Arizona Section, I was asked a question which indicates the acceleration of technical advancement. The question was: "How does an engineer at a properly keep abreast of what is new?" The fact that some 200 Arizona AIME members were at the meeting is a testimonial to the desire of these men to do just that- keep abreast. There is a great deal of talk in academic circles about the built-in obsolescence of an engineering or scientific education, too. About 100 commencement speakers every spring are sure to admonish the graduates that education is a continuing thing. Mining engineers are a small fraternity. We keep informed by talking to one another. Talking shop is valuable but there is no substitute for reading.

Jan 1, 1970

Ever since the problem of mine pollutant waters has been under consideration, different mining methods have been investigated to abate the pollution problem. Two such methods which have been reported are inert gas operation and revised mining methods.

Jan 1, 1970

By R. F. Lynch, J. D. Wood

The Al-1.0 pct Mg alloy 565 7 was studied using optical microscopy and electron microprobe X-ray analysis. Constituent particles were found to exist inter-dendritically in the as-cast material in a region of precipitate free a -aluminum. Five phases besides a fine precipitate and a-Al were identified in the cast structure: Fel3, Fe2Al7, Mg2Al3, CUMgAl2, and Cu2FeAl7. Thermal treatments conducted for 100 hr at 1180°, 1130°, 1080°, 1030°, 980°, and 880° F revealed a general dissolution and spheroidization of the in-terdendritic constituent network observed in the cast structure. The principal constituents present in the thermally treated structures were FeAl3 and Fe2Al7 with the relative amount of Fe2A17 to FeAl3 increasing with a decrease in the treatment temperature. The phases Present in the wrought structure were identical to those observed after the thermal treatments, with the constituent particles strung out in the direction of rolling. ALLOY 5657 is a nonheat-treatable commercial purity Al-1.0 pct Mg alloy utilized extensively because of its bright finishing characteristics. This investigation was conducted to determine the constituents present in 5657 alloy, and to study the effect of extended thermal treatments on morphology. Numerous studies have been carried out to establish the equilibrium diagrams for various aluminum systems,1-3 with phase identification based on X-ray analysis, morphology, and the etching response of relatively large particles. Phragmen4 conducted a study of the phases in aluminum eutectic systems and compiled a "corrected" table of etching responses, drawing on his work plus that of Schrader,5 Keller and Wilcox,6 and Mondolfo.7 A review of the original work of Keller and Wilcox, and Mondolfo, which was concerned with the constituents found in commercial alloys, reveals that in numerous cases their etching responses differ from those reported by Phragmen and from each other. These inconsistencies may occur because a specific constituent will react to a given etch in a varying manner depending upon its size, the elements dissolved in the phase, the other constituents surrounding a phase, and the solute content of the matrix. Work with a commercial orientation was conducted on alloys 2024 and 3003 by Sperry8,9 and on alloy 3003 by Barker,10 where the relationship between the phase diagram and the nonequilibrium structure of an alloy was examined. Backerud11 investigated the A1-Fe binary system and found that at high cooling rates the equilibrium eutectic reaction forming a-A1 and FeA13 is replaced by another lower temperature eutectic reaction forming a-A1 and metastable FeAl6, a constituent first identified by Hollingsworth et al.12 Most of the above mentioned studies were conducted on materials having a significantly greater alloy content than 5657 alloy, where the relatively small size and sparse distribution of second phase particles hinders the process of identifying constituents. EXPERIMENTAL PROCEDURE Material with a composition as given in Table I was examined in the as-direct chill cast, hot rolled and cold rolled conditions, and after thermal treatment of the cast structure. Thermal treatments were terminated by a water quench. Microscopic examination was conducted under various lighting conditions following the application of standard etchants as specified in Table 11. A semi-quantitative electron microprobe X-ray analysis was conducted for Al, Mg, Fe, Cu, Si, Zn, and Ti. RESULTS AND DISCUSSION Microstructure of the As-Cast Material. Particles of second phase material were found to exist inter-dendritically, principally in regions of precipitate free a-Al, as illustrated in Fig. 1. Adjacent to the ingot edge was a region of inverse segregation, resulting in an increased amount of second phase material containing large sized particles which aided in phase identification. Phase Identification. Cast Structure. Five phases besides a-Al and a fine precipitate were identified using optical microscopy and electron microprobe X-ray analysis, as presented in Tables II and III, respectively. FeA13 and Fe2A17 are often found with Fe2A17 forming a sheath around the core of FeAl3, resulting from an incomplete peritectoid reaction. These phases have a nearly identical appearance under white light, although they are easily differentiated under crossed polarizers, as characteristically illustrated in Figs. 2(a) and 2(b), respectively. Microprobe analysis con-

Jan 1, 1970

By M. Sheffield

This paper presents a technique lor predicting the flow of oil, gas and water through a petroleum reservoir. Gravitational, viscous arid capillary lorces are considered, and all fluids are considered to be slightly compressible. Some theoretical work concerning the fluid flow in one-, two- and three-space dimensions is given along with example performance predictions in one- and two-space dimensions. INTRODUCTION Since the introduction of high speed computing equipment, one of the goals of reservoir engineering research has been to develop more accurate methods of describing fluid movement through underground reservoirs. Various mathematical methods have been developed or used by reservoir engineers to predict reservoir performance, 193-5,7,8 The work reported in this paper extends previously published work on three-phase fluid flow (1) by including a rigorous treatment of capillary forces and (2) by showing certain theoretical mathematical results proving that these equations can be approximated by certain numerical techniques and that a unique solution exists. DISCUSSION The method of predicting three-phase compressible fluid flow. in a reservoir can be summarized briefly by the following steps. 1. The reservoir, or a section of a reservoir, is characterized by a series of mesh points with varying rock and fluid properties simulated at each mesh point. 2. Three partial differential equations are written to describe the movement at any point in the reservoir of each of the three compressible fluids. All forces influencing movement are considered in the equations. 3. At each mesh point, the partial differential equations are replaced by a system of analogous difference equations. 4. A numerical technique is used to solve the resulting system of difference equations. Capillary forces have been included in two-phase flow calculations.1,4,8 The literature, however, does not contain examples of prediction techniques for three-phase flow that include capillary forces. Where capillary forces are considered, each of the three partial differential equations previously discussed has a different dependent variable, namely pressure in one of the three fluid phases. Therefore, three difference equations must be solved at each point in the reservoir. Where large systems of equations must be solved simultaneously, an engineer might question whether a unique solution to this system of equations actually exists and, if so, what numerical techniques may be used to obtain a good approximation to the solution. It is shown in the Appendix that a unique solution to the three-phase flow problem, as formulated, always exists. It is also shown that several methods may be used to obtain a good approximation to the solution. The partial differential equations and differenceequations used are shown in the Appendix. Matrix notation has been used in developing the mathematical results. Two sample problems were solved on a CDC 1604. They illustrate the type of problems that can be solved using a three-phase prediction technique. SAMPLE ONE-DIMENSIONAL RESERVOIR PERFORMANCE PREDICTION A hypothetical reservoir was studied to provide an example of a one-dimensional problem that can be solved. Of the several techniques available, the direct method of solution as shown in the Appendix was used. The reservoir section studied was a truncated, wedge-shaped section, 2,400 ft long, with a 6&apos; dip. (A schematic is shown in Fig. 1.) This section was represented by 49 mesh points, uniformly spaced at 50-ft intervals. The upper end of the wedge was 2 ft wide, and the lower end was 6 ft wide. The section

Jan 1, 1970

By G. M. Swinkels

It is generally accepted, that oxygen is a necessary reagent for the flotation of galena with xanthate. Recent measurements have shown (1) that under plant conditions oxygen may be in a short supply to the extent that it limits the rate of flotation. Thus, it becomes important to define the exact role of oxygen and establish a model for the rational design and control of flotation separations, involving oxygen as a reagent. All theories or, the flotation of galena assign oxygen the role of an oxidant. However, they disagree on a number of questions: 1) Is the galena or the xanthate being oxidized? 2) Is a lead dixanthate or dixanthogen the actual collector? 3) Is the oxidation process in which oxygen participates of a chemical or an electrochemical nature? The last question arises from the observation (2) that an anodic bias as well as oxygen will make a galena surface hydrophobic in the presence of xanthate. Theories which are based an the premise that the influence of oxygen is of an electrochemical nature offer elegant models of galena flotation. However, full advantage has not been taken of available electrochemical techniques to discriminate between theories and this is the area towards which this research has been directed (3).

Jan 1, 1970

By E. E. Mason

The Canadian National Railway system is completing construction of the first major tunnel in North America to use the coarse-aggregate (+ ½ -in.) shotcrete technique of primary support and lining. The tunnel was driven 29 X 20 ft in cross section, 10,760 ft long, passing under an industrial and residential area of Vancouver. With the exception of 1400 ft in soil (mainly impervious tills), the tunnel passes through a very young series of flat-lying sedimentary beds, to a large extent so incompletely consolidated as to fall apart on exposure. For a conventional steel-support system, it was estimated 8 WF, 28-lb steel should be used at 5-ft centers. Cost of erection including lagging would amount to $120 per linear ft of tunnel at 304 per lb. With 8-in. concrete cover on the steel, lining would cost $280 per linear ft at $82 per cu yd. Thus, minimum cost of support and lining would have amounted to $400 per linear ft. It is now estimated that at least 90% of the rock tunnel would have required support and 100 % required lining. Specified shotcrete support was 6 in. in the arch and 4 in. in the walls. Cost of this work was roughly $100 per linear ft. In addition, another $10-$12 per ft has been incurred in drainage and waterproofing wet areas and in measures to correct experimental and operational errors, thus finalizing the support as a lining (Fig. 1). The tunnel was driven three shifts five days weekly, no blasting being allowed by city ordinance between midnight and 7.00 a.m. A six-drill jumbo was used to drill a 10-ft round, 110 holes blasted three times daily. A 2-in. layer of shotcrete was applied to the newly blasted arch commencing within 45 min of blasting. This was done from a flying deck that extended over the muck pile from the jumbo (Fig. 2). Also during the mucking cycle, the preceding incomplete arch support was brought up to 6-in. specification. The walls were sprayed 4 in. thick during the drilling cycle (Fig. 3). The shotcrete machines and aggregate bins were mounted on the jumbo.

Jan 1, 1970

By N. G. W. Cook

At present, tunnels can be driven in rock by either of two essentially different techniques, in one of which rock-breaking is accomplished by drilling and blasting and in the other by mechanical loading. The methods based on these techniques are comparable in terms of the rates at which tunnels may be advanced, although they differ widely in their range of applicability to different types of rock and lengths of tunnel. The method based on drilling and blasting has reached a high degree of development. It is applicable to even the hardest rocks and rates of advance in excess of 50 ft per day (fpd) are attainable. The main disadvantages of this method are that it involves a sequence of operations punctuated by blasting and that it is relatively uncontrolled, resulting in overbreaking the tunnel profile and damage to the surrounding rock. However, its flexibility, mobility, and low capital cost constitute real advantages in many situations, such as those involving short lengths of tunnel or low rates of advance. Tunneling machines based on mechanical breaking of the rock are a more recent development. They offer a continuous and controlled means of tunneling capable of rates of advance in excess of 100 fpd under favorable conditions. However, these machines weigh many tens of tons and consume several hundred horsepower, so that they are costly and lack mobility. At present, their applicability is limited to long tunnels in relatively soft rock where the high rates of advance and tunnel quality can offset their onerous capital cost. Many situations exist in which the superior quality of a machined tunnel and freedom from blasting would be real advantages, but where the rock is either too hard for existing machines or the length of the tunnel does not justify their capital cost: What are the possibilities of developing cheaper, more flexible, and mobile tunneling machines? Most existing tunneling machines fragment all the rock at the tunnel face to facilitate its disposal. If a machine were used to cut only the profile of a tunnel as one of a sequence of operations, it would be required to break

Jan 1, 1970

By John W. Bader

Probing a mineralized area with a core drill to find out what&apos;s there is fundamentally a simple task, but a costly one. Quite commonly it costs $10, and sometimes more, to extract and assay each foot of drill core obtained. Yet, it is not unusual today to drill hundreds of holes on one mineral property. The initial objective of such probing is almost always simply to determine the potential worth of the ore- body, if any exists, and the question naturally arises: How little sampling is enough for this determination? The mathematics of statistics infer accuracy of estimates largely from the sheer number of samples taken. Mineral exploration usually involves accumulation of large numbers of samples, and thus it is usually not difficult to place narrow confidence limits on either side of the estimated average grade of a sampled orebody. The determination may, or may not, be as accurate as the derivations imply. If it is not, the fault is probably one of misapplication and not with the statistical processes themselves. Un- fortunately, indications are strong that the ordinary statistics of sampling usually cannot be applied to orebody exploration samples with actual attainment of the accuracy of estimate that they express mathematically. For this reason, a more deductive, less mathematical analysis of the sampling may well be worthwhile.

Jan 1, 1970

By William G. Fricke

MaCROSEGREGATION, as distinct from microseg-regation, is often inverse in nature. That is, the eu-tectic solute elements, which are expected to be con-

Jan 1, 1970

By N. K. Bohidar

Evaluation of the stability of a structure under given boundary conditions requires accurate knowledge of the state of stress as well as the mechanism of failure at the critical state of stress. This paper represents a part of the research done by N. K. Bohidar during 1965-1968 for his Ph. D. research in Mining Engineering at the University of Utah. It summarizes the determination of internal stress and failure phenomena around cylindrical openings in viscoelastic media subjected to lateral restraint and vertical uniaxial load. The conditions of lateral restraint and viscoelastic nature of the media represent conditions associated with subsurface openings in rocks. The financial assistance provided to the project from the University of Utah Research (Uniform School Fund), W. C. Browning Scholarship Fund, Earth Science Research Fund, and D. C. Jackling Loan and Scholarship Fund is gratefully acknowledged. The authors also acknowledge the assistance of S. Siugh, W. Jones, and K. McCarter during the project.

Jan 1, 1970

By G. H. Keith

A vanadium-base alloy consisting of the following elements in weight-percent--molybdenum, 20; titanium, 10; carbon, 0.1; silicon, 0.5; and yttrium, 0.5--had exceptionally high strength at temperatures up to 1,200° C. This alloy was capable of fabrication to sheet of ~ 1 mm thickness by a combination of hot swaging and hot and warm rolling. In the warm-rolled condition at ambient temperature, its ultimate tensile strength was 1,205 MN/m2. The strength at 1,200° C was 150 MN/m2. Within the temperature range of 25° to 1,200° C, the ductility of the alloy as measured by elongation increased from 4 to >90 percent. Strengthening was achieved by both solid-solution and dispersed-phase mechanisms. Alloys of 20 percent molybdenum and 10 percent titanium were stronger than the other molybdenum-titanium alloy compositions tested. Strength was increased 15 percent in the temperature range of 25° to 800° C, with no accompanying loss in ductility, by the addition of 0.5 percent silicon. Workability was improved by additions of 0.25 and 0.5 percent yttrium.

Jan 1, 1970

By R. J. Fruehan, F. D. Richardson

Electrochemical measurements have been made of the activity of oxygen in copper and its alloys with silver and tin at 1100" and 1200°C. The galvanic cell used was Pt, Ni + NiO/solid ellectrolyte/[O] in metal, cermet, Pt The results do not support any of the equations so far designed for predicting the activities of dilute solutes in ternary solutions from activities in the corresponding binaries. If, however, a quasichemical equation is used with the coordination number set to unity, agreement between observed and calculated activities shows that this empirical relationship can be useful over a fair range of conditions. SEVERAL solution models have been proposed for predicting the activity coefficients of dilute solutes in ternary alloys from a knowledge of the three binary systems involved. Alcock and Richardson1 have shown that a regular model, and a quasichemical model,&apos; in which the dissolved oxygen is coordinated with eight or so metal atoms, can reasonably predict the behavior of both metal and nonmetal solutes when the heats of solution of the solute in the separate solvent metals are similar. But when this is not so, neither model gives useful predictions unless coordination numbers of one or two are assumed. Wada and Saito3 subsequently adopted a similar model to derive the interaction energies for two dilute solutes in a solvent metal. Belton and Tankins4 Rave proposed both regular and quasichemical type models in which the oxygen is bound into molecular species, such as NiO and CuO in mixtures of Cu + Ni + 0. However, their models have only been tested on systems in which the excess free energies of solution of the solute in the two separate metals differ by a few kilocalories. Ope of the reasons why more advanced models have not been proposed is because few complete sets of data exist for ternary systems in which the solute behaves very differently in the two separate metals. For this reason measurements have been made of the activities of oxygen dissolved in Cu + Ag and Cu + Sn. Measurements on both systems were made by means of the electrochemical cell, Pt, Ni + NiO/solid electrolyte/O(in alloy), cermet,Pt [1] The activity of oxygen was calculated from the electromotive force and the standard free energy of formation of NiO, which is accurately known.5 Before investigating the alloys, studies were made of oxygen in copper to test the reliability of the cell and to check the thermodynamics of the system. Of the previous studies those by Sano and Sakao,6 Tom-linson and Young,7 and Tankins et al.8,7 have been made with gas-metal equilibrium techniques; those by Diaz and Richardson,9 Osterwald,10 wilder," Plusch-kell and Engell,12 Rickert and wagner,13 and Fischer and Ackermann14 have been made by electrochemical methods. EXPERIMENTAL The apparatus employed was the same as described previously,9 apart from slight modification. The molten sample of approximately 40 g was held in a high grade alumina crucible 1.2 in. OD and 1.6 in. long. The solid electrolytes were ZrO2 + 7½ wt pct CaO and ZrO2 + 15 wt pct CaO; the tubes 4 in. OD and 6 in. long were supplied by the Zirconia Corp. of America. They were closed (flat) at one end. In one experiment with Cu + O, both electrolytes were used in the cell at the same time. The reference electrodes inside the electrolyte tubes consisted of a mixture of Ni + NiO. They were made by mixing the powdered materials and pressing them manually into the ends of the tubes, with a platinum lead embedded in them. The tubes were then sintered overnight in the electromotive force apparatus at 1100°C. By sintering the powders inside the tubes (instead of using a presintered pellet9) better contacts were obtained between the electrolyte, the powder, and the platinum lead. Troubles arising from polarization9 were thus much reduced. The electromotive force was measured by a Vibron Electrometer with an input impedence of 1017 ohm; the temperature was measured with a Pt:13 pct Rh + Pt thermocouple protected by an alumina sheath. The couple was calibrated against the melting point of copper. The cermet conducting lead of Cr + 28 pct Al2O3, previously found to be satisfactory9 for use with Cu + 0 was also found satisfactory with Cu + Ag + 0 and Cu + Sn + 0. Superficial oxidation was observed, but it did not interfere with the working of the cell. The reaction tube containing the cell was closed at each end with cooled brass heads and suspended in a platinum resistance furnace. The tube was electrically shielded by a Kanthal A-1 ribbon which was wound round it, and the ribbon was protected by a N2 atmosphere between the furnace and the reaction tube. The cell was protected by a stream of high purity argon which was dried and passed through copper gauze at 450°C and titanium chips at 900°C. All the metals used were of spectrographic standard. Procedure. In studies of the system Cu + 0, be-

Jan 1, 1970

By J. D. Hunt, R. J. McDonald

It is proposed that extensive fluid motion occurs between the dendrites of a Partially solid casting and it is suggested the A segregates in steel castings are a direct result of this motion. The fluid flow arises because of density differences between liquid ahead of the dendrites and the interdendritic liquid. Experiments are described on a model system investigating this fluid motion. The importance of interdendritic fluid flow is discussed with reference to longitudinal segregation. SERIOUS macro segregation is often found in large killed steel ingots. Among the most common segregates are those known as A and V, Fig. 1. The A segregates are arranged over the surface of cones, the wide parts being at the base of the ingot. The A segregates are pencil like in shape and extend from the columnar into the equiaxed region. The V segregates are distributed over inverted cones but have a less well defined shape. They occur at the center of the ingot. Because of the commercial importance of macro inhomogenities these segregates have attracted wide-scale attention. The segregates contain alloying elements and impurities which depress the freezing temperature and are thus the last liquid to freeze. A number of explanations have been proposed to explain their presence. It has been suggested1&apos;&apos; that the segregates are the result of the equiaxed zone growing towards the columnar region together with the interaction of convection within the bulk liquid. It has also been proposed that the segregates are the result of nucleation and rapid growth ahead of the dendritic front.3 Neither of these explanations is completely satisfactory because A segregates are pencil shaped and are not found as continuous cones. In this paper an alternative mechanism is proposed, and experiments are described on a model system to determine whether the mechanism occurs in practice. It is thought that A and V segregates are not peculiar to steels but should occur in many other large castings. Fluid motion within the bulk liquid region of a casting has been extensively discussed. Little attention has been paid to fluid motion within the partially solid regions. The work415 that has been done has been mainly concerned with the fluid motion which results from the volume contraction on freezing. The volume contraction is used to explain various types of macro segregation. The present authors suggest that in many cases the fluid flow resulting from volume contraction will be small compared with that due to other causes. When the columnar region is growing, the liquid still remaining between the dendrites has a much lower temperature near the ingot walls than at the dendrite tips. The composition of the liquid in contact with solid will vary with temperature. The density of the liquid will thus vary both because of changes in temperature and composition. The layers of different density liquid will give rise to a slow but steady liquid flow through the interdendritic regions. If there is no density change with composition, the temperature gradient within the dendritic region should give rise to a downward flow between the dendrites, shown schematically in Fig. 2. When the liquid density changes appreciably with alloy concentration this motion could either be en-

Jan 1, 1970