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By M. E. Wadsworth, A. E. Lewis, R. L. Braun

Experimental results obtained in laboratory leaching studies of primary copper sulfide ore in sulfuric acid systems pressurized with oxygen are interpreted by a computerized geometric model involving the movement of a reaction zone through the ore fragments. Physical properties of the ore, including size, shape, and mineral content, are considered. The leaching mechanism involves mixed kinetics and includes a surface reaction within a moving reaction zone plus pore diffusion of dissolved oxygen through the reacted portion of the ore fragment to the reaction zone. The results are applicable to conditions that would exist in nuclear solution mining or similar processes in which the ore is converted into rubble and then inundated by a leach solution adequately supplied with oxidants. Experimental results at 90°C are correlated with the model, which includes temperature-dependent parameters.

Jan 1, 1974

By D. T. Peterson, F. A. Schmidt, J. D. Verhoeven

The velocity of mig-ration of these solutes in thorium metal due to a high amperage dc current was measured at several temperatures. All three solutes migrated in the same direction as the electron flow. Diffusion coefficients were combined with the migration velocities to predict the steady-state concentration profile. Electrotransport was shown to be an effective method of removing carbon, oxygen, and nitrogen from thorium and resistance ratios several times larger than for crystal bar thorium were achieved. However, the maxirnum attained purification was well below the predicted values, apparently due to some form of contamination. THE migration of solutes in metals when a high current density dc current is passed has been known for many years. This phenomenon has been the subject of a number of reviews published in recent years.l~* Many of the earlier investigators of electromigration of interstitial solutes interpreted the direction and velocity of migration on the basis of a charge on the solute particle. This interpretation is unclear because, in a given experiment, one cannot separate the contributions to the force moving the solute which arise from the charge on the solute in an electric field gradient and the momentum transfer from the scattering of the electrons or holes. There have been only a few quantitative measurements of interstitial migration velocities and some of these have been characterized by poor accuracy or by errors in the analysis of the experiment. The electrotransport mobilities of carbon, nitrogen, and oxygen in thorium were determined by observing the rate of movement of a discontinuity in the concentration profile. This method was used by Carlson el a~.~ to determine the mobilities of interstitial solutes in yttrium and its advantages are discussed in that paper. The specimen is essentially a pair of semi-infinite, bar-type diffusion couples. The electro-transport velocity was measured by observing the displacement of the mean concentration point in a measured length of time. The diffusion coefficients were calculated by the Grube method from the concentration profile. The transport mobilities and diffusion coefficients can be used to predict the concentration profile in an electrotransport experiment of a given time, current density, and specimen length. At long times a steady state will be reached such that the natural logarithm of the concentration of each solute varies linearly along the bar with a slope which is equal to the velocity of the migrating solute divided by its diffusion coefficient. The estimation of the purification potential of electrotransport is discussed by ~erhoeven.' A comparison of the concentration profile and the purification which should be expected from known solute velocities and diffusion coefficients with that which is obtained in an experiment can be very useful in indicating whether the maximum possible purification has been achieved. EXPERIMENTAL METHOD The apparatus used in this study consisted of a sample chamber which was equipped with two electrodes, a sight glass, and a flange for mounting to a high-vacuum system capable of obtaining pressure of 2 x lo-? Torr. The chamber was made of stainless steel and was 4 in. in diam and 6 in. long. The seal between the electrodes and the chamber was made with "0" rings and compression bushings. The thorium specimens were threaded and screwed into tantalum "U"-shaped adapters attached to the ends of the electrodes. This arrangement is shown in Fig. 1

Jan 1, 1967

By J. B. Newkirk

IN 1939 Bitter and Kaufmann1 suggested that iron, precipitating from a copper-rich, Cu-Fe solid solution, appears initially as coherent particles of r-Fe which transform to the body-centered-cubic form of iron when the alloy is cold worked. Since then there has been considerable discussion, supported only by indirect evidence, regarding the validity of the concept. For example, Reekie, Hutchison, and Hether-ington2 interpreted the changes in electrical resistance accompanying the aging of Cu-Fe specimens in terms of a coherent 7-Fe precipitate which transformed to the incoherent a-phase during long aging or cold working. Greninger- ound that Cu-Fe alloys which had been water quenched from 1050" and then held at 650°C for 3 hr changed from weakly to strongly ferromagnetic as the aged wire was subsequently cold worked. He also found diffraction lines corresponding to body-centered-cubic iron in Debye-Scherrer patterns given by aged and worked specimens but lines corresponding to only one face-centered-cubic phase in specimens which had been aged but not worked. Knoppwost,' and later Cech and Turnbull,5 found that aged Cu-Fe specimens showed a slight increase in ferromagnet-ism after they had be? cooled in liquid nitrogen. Very recently Denney6 followed the kinetics of the precipitation reaction as indicated by the saturation magnetization, hardness, and diffuse X-ray effects. The experimental results reported by all of the authors mentioned above are readily explained in terms of the Bitter and Kaufmann concept. However, most of the evidence is indirect when used to define the structural changes involved. It was the aim of the present investigation to determine the mechanism of precipitation of iron from a Cu-Fe solid solution in the light of available published information and with additional new and more direct experimental data. Experimental Method At 1060°C copper will contain up to 3 atomic pct Fe in equilibrium solid solution.7 The solvus slopes rapidly toward lower iron concentration, so that at 600°C only about 0.5 pct Fe remains in solution at equilibrium. Below the eutectoid temperature (850°C), the iron-rich phase in equilibrium with the copper-rich solid solution consists of body-centered-cubic a-Fe. Above 850 °C the equilibrium iron-rich phase is face-centered-cubic r-Fe. The alloy to be studied was made by melting electrolytic iron and OFHC copper by induction under vacuum in an Alundum-lined crucible. The metal was held molten for about 5 min, after which time the power was turned off and the crucible was tipped about 70" to promote directional solidification. The resulting ingot, containing 2.5 wt pct Fe by analysis, was clean, large grained, and free of gross segregation. Slices % in. thick were cut from the ingot, rolled to 1/8 in. in thickness, homogenized in hydrogen at 1060°C for 24 hr and, finally, quenched in cold water. Specimens for all subsequent tests were made from these slices. Squares measuring about 1 cm on a side were cut from the slices to make specimens for studying hardness and microstructure. Wires (0.020 in.) for the Debye-Scherrer survey were drawn from 1/8 in. sq rods which had been cut from the homogenized slices. Large crystals for observing diffuse X-ray diffraction effects were prepared by mechanically

Jan 1, 1958

By Raymond B. Ladoo

Abrasives include the substances, natural or artificial, that are used to grind, polish, abrade, scour, clean or otherwise remove solid material, usually by rubbing action but also by impact (sandblasting, for example). They do not include abrasive tools-for instance, lathe tools and files-or polishing agents such as waxes, which act by filling pores. Detergents and cleaners whose action is chemical rather than physical are omitted although some chemical-action polishes and cleaners may also contain solid abrasives; for example, many automobile and metal polishes. General Considerations The most important physical properties of materials that qualify them for use as abrasives are hardness, toughness (or brittleness), grain shape and size, character of fracture or cleavage, purity or uniformity. For making bonded grain abrasives such as grinding wheels, additional important factors are stability under high heat and bonding characteristics of grain surfaces. The economic factors of cost and availability are always important. No one single property is paramount for any use. For some uses extreme hardness and toughness are needed, as in diamonds for drill bits; for others, the factors of greatest importance are hardness and ability to break down slowly under use, to develop fresh cutting edges when grains become worn-for example, in garnet for sandpaper, neither highly cleavable or friable grains nor extremely tough grains are wanted. For still other uses, great hardness is objectionable; for example, abrasives for dentifrices and for glass-cleaning soaps. For the most efficient use in the more critical applications, the different types of abrasives are rarely completely interchangeable; thus, while crushed quartz and garnet are both used in sandpaper, the papers are not at all interchangeable in their use applications. In the last analysis, the choice of a high-grade abrasive depends upon the quality and quantity of work done by the abrasive per unit of cost. Initial cost of an artificial abrasive. may be much greater than that of a natural abrasive but the artificial abrasive may do so much better work than the natural one, and do it so much faster, that the ultimate cost will be less. It is on this basis that artificial abrasives have largely replaced natural abrasives for grinding metal. Classification Abrasives may be divided into two general classes, natural and manufactured. The former includes all rocks and minerals used for abrasive purposes without chemical or physical change other than crushing, shaping or bonding into suitable forms. Manufactured or artificial abrasives are made either by heat or chemical action from metals or mineral raw materials. On page 2 is a list of the most important abrasives, classified as to inherent types and as to forms in which they are used industrially. For most types of use there are manufactured products that can be substituted for the natural products, usually at higher initial

Jan 1, 1960

By R. C. Hassinger, D. V. von Rosenberg

Transverse dispersion has received considerably less treatment in the literature than has longitudinal dispersion. Different methods for determining transverse dispersion coefficients have been used in different investigations, and the results obtained have not been consistent enough to permit accurate generalizations as to the effect of various physical parameters on the magnitude of these coefficients. A numerical solution to the differential equation describing transverse dispersion in the absence of longitudinal dispersion was obtained to enable one to calculate the dispersion coefficient from experimental results. The more general dispersion equation including longitudinal dispersion also was solved numerically to give quantitative limits of a dimensionless group within which the assumption of negligible longitudinal dispersion is justified. Possible experimental procedures were examined, and one utilizing a cylindrical packed column was chosen for the determination of transverse dispersion coefficients. Values of these coefficients were determined for a system of two miscible organic fluids of equal density and viscosity, for two sizes of packing material over a wide range of flow rates in the laminar regime. The dispersion coefficient was found to decrease, for a constant value of the product of packing size and interstitial velocity, as the size of the packing material particles increased. INTRODUCTION Longitudinal dispersion has received extensive treatment in the literature, and consequently is better understood than its orthogonal counterpart, transverse dispersion. Many mathematical models of dispersion processes assume that transverse dispersion is rapid enough to damp out any radial** concentration gradients and therefore may be neglected. Laboratory and production results, however, indicate that this is a poor assumption.l,2 Various experimental procedures for determining transverse dispersion coefficients have been used in previous investigations, but the results have generally been expressed by similar correlations. The transverse dispersion coefficients obtained, however, have often varied considerably for given values of the correlation parameters. We feel that further experimental determinations of transverse dispersion coefficients will help alleviate some of the inconsistencies in these empirical correlations. One assumption implicit in all previous investigations is that of negligible longitudinal dispersion in the experimental system. An attempt to justify this assumption often is made using intuitive reasoning, but it is apparent that this reasoning must break down as the condition of zero flow rate is approached. A mathematical examination of the equations describing the system yields physical limits outside of which the assumption of negligible longitudinal dispersion is invalid. BACKGROUND In a porous medium, the "effective molecular diffusivity" De is less than the molecular diffusivity D measured in the absence of a porous medium, due to the tortuous path which a diffusing molecule must travel. Various authors3-5 have reported values of the ratio De/D in the range of 0.6 to 0.7. When there is fluid flow within the porous medium, mass transfer occurs by convective dispersion as well as by molecular diffusion. These are separate phenomena and can be treated as such on a microscopic scale. However, the mathematical complexity is such that only extremely simple geometries could be considered, and the results hardly would be applicable to the complex geometries existent in actual porous media. A more

Jan 1, 1969

By K. E. Gray, M. S. Seth

Equations of elasticity for transversely isotropic, axisymmetric, homogeneous, porous media exhibiting pore fluid pressure were formulated. Using an analogy between thermal and porous body stresses, it was shown that the solution for a transversely isotropic porous body may be obtained by incorporating body forces and the stresses due to a boundary load into the corresponding solution for the thermal stress problem. Equations of elasticity ad the thermal analogy method were used to determine transient horizontal, tangential, and vertical stresses and radial displacement in a semi-infinite cylindrical region when either a constant pressure or a constant rate of flow is maintained at the wellbore. The vertical and tangential displacements are zero from the conditions of the problem. A numerical analysis was made of the solutions obtained by using a digital computer to determine the relative influence of each system variable. Considering rock as a porous body with internal fluid pressure generally gives results significantly different than considering the rock to be nonporous; the directional character of rocks leads to significant differences as compared to results based upon the common assumption of isotropy. Stress gradients are high near the wellbore but die out away from the well. Radial stresses are compressive or neutral, whereas tangential stresses are tensile, neutral or compressive, depending upon the boundary conditions and physical properties of the system Vertical stresses are compressive for an unbounded system. For constant wellbore injection rate, the vertical stress is proportional to the rate of fluid injection and decreases with time, whereas the radial and tangential stresses increase with time. At a given location, the radial displacement generally is very dependent upon time. INTRODUCTION A realistic appraisal of the state of stress in subsurface rock formations would be of considerable interest and use to the petroleum industry. For example, knowing the state of stress in proximity to a wellbore would be of fundamental importance in designing a fracturing operation or, more important, of clearly understanding the conditions necessary to produce rock failure of desired dimensions and geometry. Understanding conditions necessary for rock failure at the wellbore would also be of utility in a preventive sense. For example, borehole stability is an important consideration for many rock formations, and knowledge of the stress state at and near the wellbore under conditions of substantial pressure gradient due to fluid flow would be of great value. When fluid flows through a porous body which is initially at some uniform stress level, the following forces generate stresses at any point in the body. (1) Forces due to nonuniform pressure distribution. With increasing pressure the elements of a body are compressed. Such compression cannot proceed freely in a continuum when the pressure is not uniform throughout, and thus, stresses due to flow of fluid are set up. (2) Pore fluid pressure. This gives rise to normal stresses whose value at any point is the product of areal porosity and the fluid pressure. Although the fluid exerts uniform pressure, the stresses it creates in an anisotropic body may not be the same in all directions since the areal porosity in an anisotropic porous body is a direction-dependent quantity. This consideration leads to the concept of directional porosity. (3) Body Forces. The flow of the moving fluid imparts a force to the rock matrix, the magnitude of which depends upon the pressure

Jan 1, 1969

By Harmon F. Fisher

In the course of a comprehensive investigation for the development of the electrical process for the dehydration of oil-field emulsions, the writer has had an unusual opportunity to direct and execute a number of related, parallel studies concerning crude oil emulsions and extending over a period of nearly six years. Among these was an investigation utilizing the microscope for studying both the general characteristics of crude oil emulsions, the nature of their electrical charge and the action of an alternating current field in causing coalescence of the finely dispersed, more or less permanently suspended, emulsion particles into larger droplets of such mass that subsequent dehydration would follow by the ordinary process of settling, further agglomeration of the water droplets and, finally, separation into commercially dry, pipe line oil and a clean water discharge. It is not the purpose of this paper to enter into a detailed discussion of the highly specialized subject of microscope technique, nor into a theoretical discussion concerning the origin of the electrical charge on the emulsion particle or concerning the mechanism of the electrical phenomena occurring during the electrical treatment of oil-field emulsions. In a short paper of this character one can hope to touch on only a very limited discussion of the theoretical aspects of crude oil emulsions. The subject of emulsions and colloids is comprised in a comparatively young science in which, however, very rapid progress is being made and consequently it is undergoing many changes; a tentative conclusion valid today may be overthrown tomorrow. Nor would it be a simple science even if it were no longer undergoing this rapid progress; a thorough study of emulsions is based upon a knowledge of such fundamental subjects as molecular structure, ionization and other electrical phenomena, surface chemistry, surface and interfacial tension phenomena, viscosity and other factors too numerous to discuss here and the fundamental theories of which are still undergoing more or less change. Therefore this paper will confine itself largely to a generally descriptive discussion, a sufficiently detailed outline of the microscope technique and a brief comment on

Jan 1, 1931

By Cyril Smith

FOR several years an investigation has been in progress in the research laboratory of The American Brass Co. to determine the thermal and electrical conductivities of most copper alloys of commercial importance and several of scientific interest. This paper contains such data on the binary alloys of copper with silicon, aluminum, manganese and nickel, and on a large number of ternary or more complex alloys. Some inter-esting general relationships between the thermal and electrical conductivi-ties for all copper alloys at all temperatures are pointed out. The data for the copper-zinc, copper-phosphorus and copper-tin binary systems have already been published1,2 ? except for the electrical conductivity at 200° C., which is given in the appendix of this paper.

Jan 1, 1935

By Alden B. Greninger

THE study of mosaic structure of crystals1 has been confined until recently to the field of theoretical physics Crystallographers, in general, have neglected the subject, although X-ray crystallographers constantly make use of formulas for intensities of X-ray reflection as modified by mosaic structure Work on mosaic structure has centered chiefly on the task of proving or disproving the secondary-structure theory of Zwicky,2 and very little attention has been paid to the visible imperfections of crystals A Goetz has been responsible for most of the supposed experimental confirmations of Zwicky's theory 3 On the other hand, Smekal,4 and Orowan,5 among others, maintain that these is neither theoretical nor experimental evidence to substantiate Zwicky's secondary structure

Jan 1, 1935

By Tokio Yanagida

Major parameters relating to the operating of the conventional calcine-charged reverberatory f'ce process such as distribution coefficients of major elements among slag, matte, blister, and gases, temperatures and weights of intermediates, and heat losses of furnaces were measured and determined. A computer program to estimate heat and material balances at the process was prepared utilizing these data, showing a good agreement with actual results.

Jan 1, 1984

By T. O. Anderson, E. J. Stahl

Tests to increase knowledge concerning the process of hydraulic fracturing have been performed on three wells in the Allegheny field in western New York. The fracture orientation and its physical appearance at the well-bore was determined by impression packers run at appropriate times throughout the program. Fract~tre azi171uth and its dimensions thus determined were compared to the rock properties and treatment conditions. Logs to provide data concerning rock properties and to improve identification of vertical fractures were run before each step of the fracture treatment. Pressure osc~illu~iot~s were studied after each phase of tile treatments surface pressures during treatment. These measurements show that subsurface pressures exhibit many of the same characteristics as surface pressures during treatment of a well; however, transient pressures are dampened and deelayed in time at the bottom of the well when COmpared with surface pressures. Data obtained from this study provides a means to help locale and determine orientation of vertical fractures made in the open wellbore. Although these rests were performed in only one area, much of the information gained may be applied to fracturing programs in orher areas. INTRODUCTION In this study, various tests were made to provide data to better understand formation fracturing in situ. The reservoir studied is the Richburg oil sand which is a part of a series of predominantly grey sandstones and shales with occasional brown sandstone layers, known as the Caneadea unit of the Canadaway group of Upper Devonian age. Average physical characteristics of 12 cored wells in this area are 13-ft thick gross sand formation, 12-ft thick net sand. 1.7 md permeability, 11 percent porosity, 44 percent oil saturation (before secondary recovery) and 16 percent water saturation (before secondary recovery). This particular area of the Allegheny oil field was originally drilled prior to 1890. The first waterflood secondary recovery attempt was made in 1929. The present sustained waterflood development began in 1951 and is being carried out on a 4.5 to 5-acre spacing. Objectives of these tests were to (I) study fracture azimuth and dimension in relation to rock properties and treating conditions, (2) improve fracture identification techniques, (3) compare surface and subsurface pressure during all phases of treatment and (4) compare the periods of the fluid column oscillations occurring after each phase of treatment. Although the areas of investigation listed appear divergent in purpose, the program was designed primarily to increase knowledge of down-hole conditions leading to rock failure and extension of the fracture thus created. TEST PROCEDURES Wells upon which tests were conducted are designated as Wells 1 through 3. Well 2 was located 440 ft north of Well 1, and Well 3 was located approximately 880 ft west of Well 1. Wells 1 and 2 were completed with cable tools, while the producing interval of Well 3 was rotary cored using fresh water as the drilling fluid to obtain oriented cores. Tests were divided into separate phases on each well as the fracturing program progressed and consisted of measurements performed prior to treatment, during and after the formation breakdown operation. during fracture treatment and after treatment. To verify location and azimuth of the fracture created, and to obtain an impression of wellbore irregularities, a packer was used (Fig. 1). This packer was lowered on tubing into the wellbore opposite the interval under study and inflated in stages to allow the impression material to conform to the wall of the wellbore. A magnetic compass was attached to the tool for orientation reference. Impressions made prior to treatment showed no existing fractures in the wells under study. Impressions made after both formation breakdown and treatment pro-

By G. O. Prickett, P. Somasundaran

An experimental progmm based on statistical principles is used for optimizing a flotation operation for the separation of minerals. In this case, flotation of sylvite from sylvinite ore with amine and starch as the flotation reagents was studied to find the optimum reagent levels at various slime levels. The experiments were first done on a two-level three-factor design. Analysis of the results showed that the interactions between various factors were significant. Hence, a first-order linear model of the flotation response would not be accurate. The two-level three-factor design was expanded into a composite design in order to test the fit of a higher-order model. Data were treated to obtain an expression for flotation response as a function of the different variables, to predict the optimum reaaent levels at various slime levels, and also to determine the path of steepest ascent. Tests around the predicted optimum and along the path of the steepest ascent were done until a near-optimum region was obtained. Exploration of the nature of the response surface in that region established the actual location of the maximum response. The optimum amine level was found to be 0.20 lb of amine per ten of ore at all slime levels, while the optimum starch level varied as a function of the slime present. Computer access at the laboratory by means of a teletype terminal on a commercial time-sharing system enabled efficient and accurate treatment of experimental data. The efficiency of experimental investigations can be improved significantly by the use of experimental design and data analysis based on statistical principles. The common approach used in experimental research is to study a property of a system as a function of "one-variable-at-a-time". Several authors'-4 have pointed out the inadequacy and deceptiveness of this method. Results obtained for the effects of a variable on the measured response of the system using

Jan 1, 1970

FREQUENTLY the careful engineer puts the word porphyry in quotation marks or precedes it with "so-called," when he writes of the Porphyry Copper mines. This is done by way of serving notice that he is aware that the term is not a precise one, though no one who is informed on the subject would in any event misinterpret it. The name originated from the fact that the rock containing the copper at Utah Copper, Morenci, Nevada Consolidated, and Braden-the first four to be developed-was in each instance known as porphyry. The term was convenient; and when Ray, Miami, and inspiration came along they fell into the Porphyry category even though the ore consisted essentially of a rock called schist instead of porphyry. The word is not inclusive enough; nor as a matter of fact is it sufficiently exclusive. Numerous copper deposits occur in porphyry rocks that are not Porphyry Coppers, paradoxical as it may seem. Desiring to be more accurate and at the same time to use a word that is in some degree descriptive, various engineers have adopted the expression "disseminated copper deposits." This alludes to the characteristic scattering of grains or specks of copper minerals more or less uniformly throughout the mass of the rock. Yet here again the implication is not entirely accurate, for the following reason: in some of the ores, the proportion of copper minerals "peppered" in the rock is small, compared with that which coats the walls of cracks and minute fissures; and that which is found as veinlets along planes of fracture. Many geologists have extended their interpretation of the term disseminated to include both types of mineral occurrence. One of the most striking features of the Porphyry ores is the intense shattering and fracturing that the rock underwent at some period or periods prior to the deposition of the copper

Jan 1, 1933

By R. W. Heckel

The growth and shrinkage rates of second-phase particles of various size distributions are analyzed in terms of five mathematical models. These models apply to various forms of diffusion-controlled growth (one model) and interjace-controlled growth (four models). The expression for diffusion-controlled growth assumes local equilibrium at the interface between the second Phase and the matrix and through the choice of the proper flux area perrnits the definition of minimum diffusion-controlled growth kinetics. The interface-controlled kinetics models consider the situations where the rate-controlling step occurs at either the interlace undergoing solution or the interface undergoing deposition. In addition, each of these interface-controlled kinetics models is analyzed for interface reaction rates which are independent of the thermodynamic activity gradient across the interface or proportional to the gradient. THE variation of the size distribution of second-phase particles in a solute-saturated matrix has been a stimulating topic for many years. Research has been carried out in this area for situations where the matrix was either liquid or solid. It is well-understood that the over-all process results in an increase in the average particle size, a decrease in the total number of particles per unit volume, and a net decrease in surface area. Greenwood1 has presented a mathematical model based upon the mass balance existing between growing and shrinking particles. His analysis is stated in terms of Fick's First Law using concentration gradients set up between particles of different size as a result of the effect of surface curvature on solubility. Greenwood's analysis indicates that the mean particle size should increase approximately as the cube root of time. Asimow2 has shown that several of the simplifying assumptions employed by Greenwood may be eliminated from this diffusion-controlled model with little increase in complexity. Lifshits and Slyozov3-5 have also considered the growth-shrinkage problem involving diffusion-controlled kinetics. Their analysis was extended to include the effects of interacting particles ("kinetic approximation"), particle shape, and elastic strains. These authors also show that the mean particle size varies as the cube root of the reaction time. wagner6 has formulated expressions for both diffusion-controlled kinetics and interface-controlled kinetics in the growth-shrinkage problem. Wagner's diffusion-controlled kinetics is based upon the same form of mass balance using Fick's First Law as used by others and is shown to be applicable to situations where kr >> D (k is the interface reaction constant, r is the particle radius, and D is the diffusion coefficient). This analysis also yields a mean particle size which varies as the cube root of time, in agreement with other workers. Wagner also developed interface-controlled kinetics to handle kr « D. This model was based upon the fact that the interface reaction rate is proportional to the interface area. Wagner assumed that the rate was also proportional to the thermodynamic activity difference, ?a, existing across the interface. Thus, the specific reaction rate at the surface of radius r was defined as k • 4nr2 . ?a. It is the purpose of the present paper to reconsider the processes of diffusion-controlled growth and interface-controlled growth in the variation of particle-size distributions as a function of time at constant second-phase volume. The analyses are formulated in a manner which permits data obtained

Jan 1, 1965

By F. A. Crossley

The titanium-rich end of the Ti-A1 system has been investigated up to 35 at. pct A1 (23 wt pet). One conzpound Ti3Al was found to occur between primary a and TiAl. It is ordered hcp with DO19 structure, it has virtually no solid-solubility range, and it has a closed maximum at about 875°C. OIL either side of the compound are a +Ti3Al two-phase fields. The limiting a1uminum solubility in primary a at the titanium-rich end is indicated to be 7.5 at. pct A1 (4.4 wt pet) at 550°C and about 6.8 at. pct Al fl wt pct) at 500°C. Quenching alloys from above the a + Ti3Al two-phase field produces the following structures with respect to alloy composition: Up to 13 at. pct A1 (7.8 wt pet), a solid solution; from 15 to 18 at. pct A1 (9 to 11 wt pct), shear transformation product or martensite; from 19 to approximately 30 at. pct (11 to 19 wt pet), submicro-scopic coherent Ti3Al in an a malvix. The twin hcp phase fields reported in the literature are the result of nonequilibrium corzdztions. Ti-A1 alloys, once partitioned by dwelling- in the a + ß phase field during either hot working or heat treatment, are extremely difjicult to homogenize at temperatures below 1000°C. Such partitioned alloys exhibit the characteristics or symptoms of two-phase materials, and may be said to suffer the "twin-phase syndrome". THE earliest investigations of the Ti-A1 system by Ogden et al.1 and Bumps et al.2 reported wide solubility of the primary solid solutions. Aluminum was reported soluble in the low-temperature allomorph to the extent of 37 at. pct (25 wt pct), and the first intermediate phase was reportedly TiA1. Somewhat later Kornilov et al.3 reported a similar diagram with phase boundaries displaced towards lower aluminum contents and higher temperatures. Beginning about this time (1956) reports in the literature made it very clear that one or more intermediate phases occurred at lower aluminum contents than TiAl.4-17 These reports included five major investigations of the titanium-rich end of the Ti-A1 diagram.4,12,14,16,17 Three of these diagrams show two two-phase fields below 37 at. pct Al, while two of them show a single two-phase field. The existence of the phase Ti3A1 is firmly established and is included in each of the diagrams, except one—that of Sato and Huang.12 The new phases are reportedly hcp and differ from primary a only slightly when disordered, and when ordered the "a" parameter is approximately one,4,12,15 two, 6-10,13,14 or four14 times that for primary a. Beyond this, however, the diagrams are remarkable for their lack of agreement. Two tacit assumptions are usually made in phase-diagram determinations of metal systems. These are: 1) equilibrium anneals bring the alloy to equilibrium or to indistinguishable closeness to it, and 2) equilibrium conditions established at elevated temperatures are either "frozen" by rapid quenching for evaluation at room temperature, or quench-transformation products are recognized as such. In the current investigation evidence was obtained that over substantial composition ranges neither of these two conditions was met in any of the more recent major investigations. I) MATERIALS, METHODS, AND TECHNIQUES The alloys of this investigation were prepared by nonc on sum able electrode arc melting. Materials used in the preparation of the alloys are summarized in Table I. The investigative tools employed were: optical and electron microscopy, differential thermal analysis (DTA), disatometry, X-ray diffraction, electron diffraction, and resistometry. Alloys for microscopic and X-ray investigations were prepared as 15-g melts. Alloys containing from 7 through 11 at. pct A1 were hot-rolled out of a furnace at 900°C, from 12 through 15 at. pct out of a furnace at 1000°C, and from 16 through 18 at. pct out of a furnace at 1125°C. Alloys containing more than 18 at. pct A1 could not be hot-rolled. The ingots were covered with Markal coating prior to hot rolling to minimize atmospheric contamination. After hot rolling, alloys containing up to 15 at. pct A1 were ground and pickled to remove 7 mils from each surface; alloys containing 16 and 18 at. pct A1 were skinned to a

Jan 1, 1967

By G. Gutzeit

METAL-ORGANIC INNER COMPLEXES AN inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity. 4,1-13 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime.) It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry,, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals.17 CHELATE-FORMING COMPOUNDS AS COLLECTORS In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxylamine (Cupferron) C6H5NO(=NONH4). Holman19 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-dioximes were generally selective collectors for nickel ores. Taurin NH2(CH2)2SO3H has been proposed for the concentration of oxidized lead ores.19 Diphenylthiocarbazone

Jan 1, 1946

By D. E. Light, J. Y. Somnay

The use of alkyl acid phosphates and their alkali salts as collectors for the uranium minerals brannerite and uranothorite was investigated. In particular a detailed flotation study was carried out using isooctyl acid phosphate as a promoter. Tests were conducted on an Elliot Lake ore analyzing 0.11% U 3 O 8, chiefly as brannerite, and approximately 9% pyrite. Pyrite was floated with conventional reagents; the flotation of brannerite from the sulfide tails was studied to determine the optimum pH and pulp density to employ with isooctyl phosphate. 4 uranium recovery of over 90% was possible with a selectivity index of 8.95 when these tails were floated at 17% solids and a pH of 1.7. The effect of various modifying agents was also investigated. Aluminum sulfate, lactic acid and sodium silicate improved the selectivity of collection yielding selectivity indices of 9.5 to 11.5. Ferric chloride was found to be a depressant for brannerite. A Bancroft ore which analyzed 0.13% U308, and contained uranothorite was also amenable to flotation using isooctyl acid phosphate. The composite uranium concentrate obtained assayed 0.41% U308 at a recovery of 95.3% and a ratio of concentration of 3.24. Previous investigations1,2 on the flotation of brannerite, pitchblende, uraninite and/or uranothorite from various Canadian ores showed that fatty acids, including oleic acid and tall oils, petroleum sulfo-nates and alkyl acid phosphates, were suitable collectors for these uranium minerals. Additional work carried out by the Mines Branch in Ottawa on brannerite ores from the Elliot Lake area3 used the tall oil Acintol FA-1, or FA-2, as a collector. A recovery of 92% of the uranium in a concentrate which contained about 55% of the weight and assayed 0.2% U3O8 was obtained from a feed of 0.1% U308 in this latter instance. Eigeles et a1.4 carried out flotation on pitchblende ores and found that the most promising results were obtained with alkyl acid phosphates and their alkali salts as collectors. Within the homologous series of alkyl phosphates, the best flotation characteristics were displayed by isooctyl phosphates. Further, isooctyl phosphate derivatives were much less sensitive to hardness forming salts than oleic acid, enabling all flotation tests to be made with tap water. This paper describes tests employing alkyl acid phosphates for the flotation of ores containing brannerite and uranothorite. The flotation work described herein was conducted in conjunction with the development of a leaching process for Elliot Lake, Ontario, brannerite ores. In this process pyrite in the ore was concentrated by flotation and roasted, providing sulfur dioxide which was used to produce sulfuric acid in situ in a liquid-solid extraction process. A 40% conversion to sulfuric acid was indicated at a leaching temperature of 80°C; this resulted in the extraction of 93% of the total uranium after a contact period of 6 hr. A rotary kiln was used as a leaching vessel. Preconcentration by flotation was studied in conjunction with the above process to reduce the bulk of solids for leaching and, consequently, capital expenditure. The materials and methods used in this study will be described initially. Then the results will be presented in two sections, the first dealing with the brannerite ore, and the second with the uranothorite. Finally an economic analysis of the results on the brannerite material will be made. MATERIALS AND METHODS The two ore samples examined were from uranium-producing mines. One was a brannerite ore, a uraniferous quartz pebble conglomerate from the Elliot Lake area, which contained 0.11% U3O8, 4.3% S and 4.5% total Fe. Mineralogical studies of similar samples indicated the presence of quartz, microcline, sericite, pyrite and minor quantities of rutile, pyrrho-tite and zircon. The other ore was from a biotite-rich pegmatite in the Bancroft area; feldspar, quartz and biotite formed the major gangue components. Uranothorite was the principal uranium mineral; the head assay was 0.13% U 3 O 8. Preparation of Feed: The ores were crushed to —10

Jan 1, 1963

By J. E. Hanlon, S. R. Butler, R. J. Wasilewski

The temperature, orientation, and strain-rate dependence of tensile flow in single-crystal NiA1 of equiatomic composition have been investigated up to 800°C. Compression tests at room temperature have also been carried out. Optical and replica electron microscopy and X-ray diffraction methods were used to investigate the slip mechanisms. NiAl exhibits {110)(001) slip and cube slip {l00)(010) was also observed. This results in very high strength of single crystals in cube orientation. The implications of this slip mode, with the resultant small number of possible slip systems and three mutually perpendicular slip vectors, are discussed. ThE CsCl structure compounds represent a class related to the bcc elements, but their behavior is affected by three additional variables: composition (within the stability range of the compound), extent of long-range order perfection, and bonding energy. Very little data are available on the effects of these variables on mechanical properties. Rachinger and ~ottrell' suggested slip to occur along (111) in compounds of low ordering energy; in compounds of higher bond strength (>0.06 ev), they observed (110) (001) slip. As pointed out by copley,' only three in- dependent slip systems are available in the latter case; hence general deformation is impossible. Brown3 carried out a theoretical calculation of the yield-point variation with the degree of long-range order in the CsCl structure, based on the assumption of superdislocations. More general approaches, based on considerations of superlattice dislocations and antiphase domain boundaries in ordered structures, were carried out by Flinn~ and by Vidoz and Brown.' These, however, give no information on changes in the slip structure—if any—between the ordered and the disordered compounds. This aspect was investigated experimentally and theoretically by Stoloff and Davies' and by Marcinkowski and chessin7 in FeCo. The latter workers proposed the deformation behavior of the ordered FeCo to be essentially the same as that in many other bcc metals. Investigations of polycrystalline A~M~'-'O indicate considerable variation in mechanical properties with composition and test temperature. The existence of {123)(111) slip was reported in AgMg.'9'9'0 (The formation energy of this compound, presumed to be ordered at all temperatures below melting, is 4.38 cal per g-atom," i.e., 0.024 ev per bond.) The yield strength has been reported as relatively independent of temperature below 0.45 T, (where T, is the absolute melting temperature). Tensile deformation of single-crystal AgMg was also investigated by Kurf-man," who observed marked tendency to single glide on{112}(111) and {110)(111). From observations of slip lines in deformed poly-crystalline NiA1, Westbrook et a1.I3 suggested the

Jan 1, 1968

By James Ferguson

THE fact that little if anything has appeared in the technical press or in the Transactions of the Institute on the subject of roll shells proper, used in various grinding appliances such as Cornish rolls or Chilean mills, may be taken as an incentive, if not an excuse, for the present article. No attempt is made to enter into a. discussion as to the theory or mathematics of crushing as performed by rolls, the subject being treated in a general way with respect to the manufacture of roll shells 'and some salient points touching on their adaptability and wear in service. While it stands to reason that skill coupled with judgment in the mechanical design of rolls, Chilean mills or other types of grinding machinery, with special reference to strength of parts, nicety of adjustment and other mechanical features, stand for efficiency in their operation .and satisfaction in service, the exceedingly important item. of roll shells or other wearing parts entering into their construction should not be lost sight of. In other words, a well-designed piece of grinding machinery is just as inefficient in service, when equipped with poor roll shells or shells made of the wrong or an inferior grade of metal, as good roll shells made according to the best practice the steel maker knows, working on an old or antiquated set of rolls. Unfortunately there is a tendency occasionally for the machinery builder to blame the steel maker or vice versa if roll shells do not wear well or evenly, or if they break before being worn down to their ultimate thin point. There is no occasion for this attitude, as the product, of each must stand on its own merits. But it is essential that the two work in harmony since the machinery builder usually does not furnish the shells for his rolls or grinding mills, but depends on the steel maker, who makes a specialty of this rolled product, to give the particular needed element of efficiency to his machine.

Jan 9, 1914

By H. O. Hofman

In the blast-furnace smelting of lead, copper and other non-ferrous metals, the largest part of the product obtained is slag. Its formation consumes more of the heat-energy of the fuel charged than any other chemical reaction that takes place. It is therefore of importance to know at what temperatures the different slags will form, so as to be able to choose in a given case the slag that will form at the right point in the operation, will keep the products thoroughly fluid, so as to insure a satisfactory separation, and will permit the consumption of fuel to be reduced to the lowest practicable point. While practical experience has brought out in a general way the leading differences as to the formation-temperatures of Rome silica—iron —lime slags, accurate details are still wanting. The object of the investigation here described was to supply some of these.* Prominent among the men who have worked on the fusibility of silicates are Lampadius, † Sefström,‡ Berthier,§

Jan 1, 1900