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By W. C. Knopf, I. M. LeBaron

In the Carlsbad area potash is dry-mined and wet-concentrated. Wet concentration involves recircu-lation of saturated brines, with resultant difficulties of brine disposal and inherent losses in recovery through solution of the KCl. A dry beneficiation process for potash minerals would offer many advantages over present methods. International Minerals & Chemical Corp. has been working on development of a dry process for some time. This article is a progress report. Potash ores available in this country are largely mixtures of halite and sylvite contaminated with slimes and often with many sulfate and magnesium minerals. Electrostatic concentration of KCl when the contaminating minerals are in low percentage has been accomplished. Continuous production of better than 60 pct K2O concentrate from high potassium sulfate ores has not been demonstrated at the present time. Laboratory Procedure: Laboratory work on electrostatic beneficiation of potash minerals has been carried out using both pure crystals and mined ore. Electrostatic separation of the two main components of potash ore, sylvite (KCl) and halite (NaCl), is accomplished by first heat-treating the ore to allow for electric charging of the particles. Preferential exchange of' electrical charges between different mineral particles through surface contact is the principal mechanism involved. After proper conditioning of the particle surfaces, the oppositely charged minerals are dropped vertically into a horizontal electric field having a field gradient from about 5000 to 15,000 v per in. The particles are free-falling in the field. A suitable power supply is used to produce the proper total voltage for the electric field. Total required voltage is, of course, a function of electrode spacing. A typical electrode arrangement with power supply is shown in Fig. 1. In general, the total voltage on any system is 75,000 to 90,000 v. Power consumption is negligible, as leakage at insulators and corona discharge are the main losses in the system. Optimum preheat temperatures for pure material components generally are not the same as for mined minerals. Fig. 2 shows clearly that maximum recovery on a 50 pct pure KCl, 50 pct pure NaCl mixture occurs at a preheat temperature of about 600°F. In this test the preheat mixture was allowed to cool to about 225°F before dropping through the electric field. The optimum temperature for sep- aration is practically never the optimum temperature of preheat. Optimum separation for mined Carlsbad potash ores occurs when a preheat temperature closer to 900°F is used, as shown by Fig. 3, which plots percent sylvite (KCl) in the concentrate and tails as a function of preheat temperatures. Here again the ore was allowed to cool to about 225°F before separation. It should be noted that efficiency of separation increases continuously with increasing preheat temperatures until incipient fusion of the ore takes place at about 950°F. The increase in optimum preheat temperature for Carlsbad ores over the pure minerals can be traced to the effect of the clay slimes intimately associated with the mined potash. If the slimes associated with the ore are removed by washing with alcohol or other non-aqueous material, the necessity of preheating to the high temperature is removed. This temperature range has been proved critical within these limits during continuous pilot plant operation. Concentrate and tailings grade and optimum recovery also are functions of the temperature of the potash mineral particles during separation in the electric field. Fig. 4 presents data indicating that feed to the rougher pass should range between 150°F and 275°F for best results. It has been found by subsequent pilot plant work that these temperatures can be maintained in actual operation.

Jan 1, 1959

By W. O. Philbrook, K. M. Goldman, G. Derge

THIS is the third in a series of papers from the Metals Research Laboratory dealing with the transfer of sulphur across the iron-slag interface in a carbon-saturated system. The first paper' showed that the transfer obeyed first-order kinetics. The second' presented detailed evidence in support of the three-stage mechanism: FeS(Fe) FeS(slag) FeS(slag) + CaO(sing) ? CaS(slag) + FeO(slag) FeO(slag) + C ? Fe + CO. This emphasized the role of an iron-sulphur complex as the transfer agent across the interface and as an essential intermediate in the overall process. The present paper shows the influence on the process of the individual elements, carbon, silicon, manganese, and phosphorus, the alloying elements normally present and of interest in commercial blast furnace operations, aluminum, which has a pronounced accelerating influence, and nickel and copper, which are common minor impurities in the raw materials. The experimental methods and procedures for interpretation of data are the same as described earlier.1,2 Induction heated, graphite crucibles were used, and sulphur-free slag was added to the molten iron containing sulphur and the selected alloy. Slag samples were taken at regular time intervals and analyzed for sulphur and other components of interest. The authors wish to state specifically that these experiments were not intended to simulate industrial blast furnace operations. However, they do represent a study of the kinetics and mechanism of sulphur transfer at the slag-metal interface under specified laboratory control of the major variables in the system. It is believed that the results can be usefully applied to the blast furnace if consideration is given to the differences which are known to exist between the two conditions. A rigorous evaluation of the accuracy of rate studies is difficult. Recognized sources of error include sampling and analysis of both slag and metal, temperature measurement and control, selection of zero time, composition of the gaseous atmosphere over the reaction system, and extraneous sources of sulphur from the graphite crucible and reagent materials. In this study carefully standardized procedures were followed consistently in order to minimize the errors. It is believed that the reproducibil-ity of duplicate runs indicates that errors have been rendered negligible relative to the observed effects from intentional variables. For example, original experimental points for duplicate runs are shown in Figs. 1, 2, 7, etc. In most cases in this paper the drawn curves represent an average of at least two heats. The spread in sulphur values at a given time ranges from 0.02 to 0.08 pct, which is a small frac-tioi of the total values ranging up to 2 pct S in slag. In the systematic study of the influence of alloy additions, each element was added over a range of concentrations. The two slags used in this study were designated as "acid" or 1530 and "basic" or 1545. They had the nominal compositions given in Table I. Rates were measured in the temperature range 1500" to 1650°C. Data will now be presented to illustrate the various features of the study. Silicon The first alloying element examined was silicon, because its presence is unavoidable in any silicate slag system through the reaction y/2SiO2(slag) + xM?y/2Si(liq.Fe) + MxOy where M is any reducing agent such as iron or carbon. It is known that the attainment of equilibrium by this reaction is extremely slow and probably not reached in the blast furnace." The influence of silicon on the final stages of the sulphur reaction has also been studied.' It has been shown5 hat silicon increases the activity of sulphur in iron. For such reasons silicon may also be expected to influence the kinetics of the reaction. The observed effects will now be described. The general procedure was to melt 530 grams of ingot iron in a graphite crucible, 3 in. OD, 2 1/4 in.

Jan 1, 1955

By C. W. Sherman, John Chipman

IN the mathematical statement of the law of mass action, the activity of each substance consumed or produced in a reaction is used to obtain a numerical constant which is characteristic of the equilibrium of that reaction at the given temperature. The activity in many cases is equal to, or proportional to, the concentration. If this is the case, any units denoting concentrations, such as weight percentage or mol fraction, may be substituted in the equilibrium expression. It is even permissible to use mixed units provided only that each unit is that used in defining the activity of the corresponding substance. The indiscriminate use of concentration units in writing equilibrium constants sometimes leads to very erroneous results. On the other hand, what appear to be contradictory results from similar investigations often might be resolved if the activity is the quantity that is used to determine the equilibrium constant for the reaction in question. De-sulphurization serves as an important illustration. Sulphur in lron and Steel The control of the sulphur content of the finished product is one of the oldest and broadest problems in the metallurgy of iron and steel. In general, this control must be exercised through the action of a slag, and for this reason experimental studies of the distribution of sulphur between slag and metal have assumed considerable importance. Under slags of the type found in the basic open-hearth furnace the ratio (% S)/[% S] does not in general exceed about 8. Under blast-furnace conditions, however, de-sulphurization ratios of 50 to 100 are readily obtained, and under laboratory conditions using similar slags, the ratio may be as high as 400. The fact that blast-furnace metal is much more readily desulphurized than is molten steel rests upon two distinct phenomena. The first of these is connected with the slag reaction. In the open-hearth furnace, the equilibrium in the following reaction places a definite limit on the sulphur content of the slag: S + 0-- = 0 + S- - where the symbols underlined indicate elements dissolved in the liquid metal, while slag constituents are represented as ions. The high oxygen content of the open-hearth bath prevents this reaction from proceeding far enough to effect good desul-phurization. In the blast-furnace process, however, the oxygen activity is limited by the presence of carbon in the metal and in the coke bed and the controlling reaction becomes: S_+O- + C_=S- + CO(gas) [2] The second phenomenon which contributes to the easier desulphurization of blast-furnace metal is the effect of high concentrations of other elements. These elements, notably carbon, silicon, and phosphorus, increase the thermodynamic activity of sulphur several fold. As a result of this increase, the escaping tendency of sulphur from the metal phase is increased and its removal facilitated. Previous Studies It becomes, therefore, a matter of importance to determine the effects of various elements upon the activity of sulphur in the melt. The experimental approach to this problem has been made through the equilibrium between sulphur in the melt and gaseous atmospheres containing hydrogen and hydrogen sulphide. The reaction and its equilibrium constant are written as follows: S + H2(gas) =H2S(gas);K1 = -- [3] Pn2 • as where the symbol a, represents the activity of the sulphur in solution in the metal. The understanding of the chemical behavior of sulphur in steel and pig iron rests on a firm knowledge of the binary system Fe-S. A number of studies of the equilibrium have given closely agreeing results from which the activity and free energy of the dissolved sulphur may be found. The recent paper by Sherman, Elvander, and Chipman1 includes a discussion and quantitative comparison of the results of several of the significant researchesr-" on dilute solutions of sulphur in iron. The results of this study indicate that the relationship between the ratio Ph,s/p+ and the percentage of sulphur in solution is not a linear one. This

Jan 1, 1953

By E. L. Dougherty

A phenomenological theory for a one-dimensional unstable miscible displacement similar in type to the Buckley-Leverett model but including the effects of mixing is proposed An equation giving the fractional flow of pure solvent through an oil phase containing dissolved solvent is derived including the effects of gravity and nonbomogeneities. Numer ical integration of the resulting pair of nonlinear hyperbolic partial differential equations gives volumes of dissolved and undissolved solvent as functions of space and time. Parameters in the model which characterize mixing due to dispersion were determined from experimental data; the parmeters correlated with viscosity ratio. The results indicate that the rate of dispersive mixing is proportional to volumetric flow rate Incorporated into our equations were Koval's heterogeneity factor H. which characterizes mixing due to channeling. This allowed satisfactory predictions of displacement behavior observed in horizontal floods in nonhomo-geneous cores; but in most cases the values of H which we used were considerably larger than those used by Koval. INTRODUCTION It has been shownl,2,3 that for favorable viscosity ratios, the diffusion equation with convection satisfactorily describes the behavior of a miscible displacement in a porous media. Numerous attempts to develop a satisfactory mathematical description for the case of unfavorable viscosity ratio have been reported, but they have met with only partial success. These attempts, which are reviewed by oval! have taken two approaches: (1) development of a flow model akin to the Buckley-Leverett approach for immiscible displacement neglecting the effects of mixing5,6 and (2) simultaneous application of Darcy's Law for flow and the diffusion equation with a convection term for mass transfer.7,8,9 We set out to construct a mathematical model of Type 1 including, though, the effects of mixing. Based upon a set of hypotheses, we derived a pair of nonlinear hyperbolic partial differential equations which describe in a one-dimensional system the combined effects of flow and mixing. To work with these equations it was necessary to develop a fractional flow formula. The combined system was integrated numerically using the method of characteristics. In our equations the mixing process is characterized by four parameters. Three of these, labeled ß, P1 and P2, account for dispersive type mixing. The fourth is the heterogeneity factor H, proposed by Koval to account for channeling due to nonhomogeneities in the porous media. Values of the parameters which would cause agreement between theory and experiment were determined by trial-and-error for miscible floods conducted in horizontal cores of both homogeneous and heterogeneous materials. Calculations were also performed for vertical floods in homogeneous cores. The purpose of this paper is (1) to present the details of the mathematical analysis, (2) to present the results of the calculations, (3) to consider what light the results shed on the mixing process in an unstable miscible displacement, and (4) to provide a firmer foundation for the correlation technique developed by Koval for predicting the behavior of unstable miscible floods. STATEMENT OF PROBLEM The problem is to construct a mathematical model which describes in one dimension the observed behavior in an unstable miscible displacement. The approach is phenomenological in that the equations are based on assumptions which violate certain physical precepts known to apply to the displacement phenomenon. However, the assumptions do allow us to account mathematically for the more essential phenomena. The work is of value if we can quantitatively predict experimental results which heretofore could not be predicted, even though the synthetic nature of the model belies complete explanation of the observations. We assume that the system is comprised of two contiguous flowing phases. One phase, which we call free solvent, has the properties of pure solvent. We call the fraction of the pore volume occupied by this phase the solvent saturation, designated s. The oil phase consists of oil containing dissolved

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By J. Chipman, H. Towers, M. Paris

A simple radioactive tracer technique is used to measure the diffusion coefficient of calcium ion in molten slags. In a slag of 40 pct Ca0-40 pct Si0,-20 pct Al203, Dc " at 1450°C is 1.3x10-6 cm' sec-'. THE application of the principles of thermodynamics to steel and iron making problems has proved so fruitful that the kinetic approach has tended to be neglected. It seems probable that in some reactions the rate-determining step is the dif-fusivity of the reactants or of the products. But knowledge of the diffusion coefficients of the constituents of liquid slag and metal is singularly lacking. The present work was undertaken as a first step toward supplying such data for slags. Furthermore, any additional information on the physical properties of liquid slags might be expected to help in elucidating their structure. It is essentially a preliminary investigation, the course of which was determined more by the necessity of establishing a method than by the immediate intrinsic interest of the results. For example, the selection of calcium ion to be studied was dictated by the suitability of the isotope Ca45 in that it is a simple emitter with a long half-life. Of the other ions commonly encountered in slags, the isotopes of iron and manganese have relatively complex radiations as well as the normal disadvantage of requiring control of the oxygen potential of the atmosphere; Mg27 and Al29 have half-lives measured only in minutes; Si3' has a simple decay process but its half-life of 2.8 hr is too short for preliminary studies; the only useful oxygen isotope is the stable O18; and there remain only sulphur and phosphorus both of which have suitable isotopes but were rejected as being of less fundamental interest than calcium. Similarly a lime-alumina- silica slag was used in preference to calcium silicate primarily because of its low melting point and its capacity to form a glass on fairly rapid cooling. Literature Review Very few studies of diffusion in liquid silicate systems have been reported. In order to determine the origin of diopside inclusions in felspathic rocks, Bowen1 investigated the diffusion between diopside and various mixtures of albite and anorthite. Platinum crucibles were used with diopside, the heavier of the two liquids, forming the lower half of the cell and diffusion taking place against gravity. Change in concentration along the diffusion path was found by measuring the refractive index of the quenched glass. Nearly thirty years later McCallum and Barrett2 used essentially the same method to determine the diffusion coefficient of lime in lime-alumina-silica slags. In this case the interest was to find the rate-determining step in the process of slag attack on refractory materials. In an investigation of the kinetics of the sulphur reaction, Derge, Philbrook, and Goldman8 determined the diffusion coefficient of sulphur in a typical blast furnace slag by the simple procedure of melting a slag containing 2 pct S over an identical slag sulphur-free. They make no claim to a high degree of accuracy but suggest that D, is of the order of 10-6 cm2 sec-l. Other high temperature liquid diffusion studies have been concerned with metals. Holbrook, Furnas, and Joseph4 determined the diffusion coefficients of silicon, phosphorus, sulphur, manganese, and carbon in liquid iron by immersing a small carbon crucible containing pure iron-carbon alloy in a large vessel containing iron with a high concentration of the particular element. Their results were confirmed by Paschke and Hauttmann5 using a similar method. Diffusion coefficients in silicates in the glassy state have been studied by Johnson, Bristow, and Blau6 Both Na24 and Ca45 were used as tracers but only the

Jan 1, 1954

By C. L. Pillar

INTRODUCTION The location, size, character of the ore de- posit and its adjacent formations will deter- mine the mining system best used for its ex- traction. The mining system chosen will have to be engineered to suit the ore deposit and the people that will extract it. What can be done in the Philippines cannot always be accomplished in the upper Northwest Territory of Canada. Mining operations developed under a free enterprise system are planned to achieve a satisfactory return on the capital required to place them into production. Hence, the choices made in planning and developing the mining system must be dictated by sound economics. The mining system planned must favor: 1. Maximum ore extraction of the deposit with minimal grade dilution. 2. The amount of capital expenditure used to develop and equip the mine must be in harmony with the financial policy of the group yet be sufficient to provide a reliable mining system. Excessive frills and extras that are not required for efficient, safe production should not be provided. 3. Mine production costs are determined by the amount of men, material, equipment and energy used in the production process. These must be kept to minimal limits in order to insure dependable, low cost production. Extras that later are needed in the production operation can be added as required by the operator. Basically block caving is a mining system that is normally used to extract deep seated, massive, low grade deposits of copper, molybdenum and iron where stripping ratios for open cast mining are economically prohibited. The caving system is limited in its selectivity. It is a mass production type of underground ore extraction that under favorable conditions is one of the most efficient, low cost mining systems in the world today. Usually block cave mining systems are large. They are capable of producing ore at a rate of 10,000 to 100,000 tons/day from large deposits at costs that are comparable with many open cast mining systems burdened by high waste to ore ratios. Block cave mining systems differ basically in the plan of the area layout, the method of undercutting and the method of draw. The balance of the mining system is the mechanical transportation of the drawn ore to the surface, the mine supply, drainage and ventilation systems. This paper deals mainly with the methods of draw. The method of draw to be used in a block caving system dictates the development plan of the mining area, is highly influential in the method of undercutting to be employed and the supply and ventilation system to be used. There are three basic methods of draw commonly used in today's operations. They are: Gravity draw Slusher draw LHD draw The type of draw planned will have a major affect on: Capital expenditure and time required to bring a deposit into production. Productivity, efficiency and cost of the production operation. Percent recovery of the ore deposit in both tonnage and grade. Degree of production reliability Fundamentally the type-of draw used must be compatible with the physical characteristics of the deposit to be extracted and the financial position of the mining operation. The type of draw chosen must work to advantage with the size, configuration, depth, strength and fracture pattern of the deposit and its adjacent formations. It must favor the financial protection of the planned mining operation. A Gravity Method of Draw requires a finely fragmented, easy flowing product from the caving action of the deposit. To obtain the desired economic advantage the ore deposit must also have sufficient area and height of column to permit minimal development cost on a per ton basis. The gravity system re- quires the maximum amount of development openings and uses the minimum amount of mechanized equipment of all the caving systems. It is unskilled, labor-intensive and is highly sensitive to size of ore fragmen-

Jan 1, 1981

By H. M. Strong

Nickel and carbon form a metastable nickel-nickel carbide eutectic system which was ohsen)able by freezing latent-heat arvests at pressures 210 khars. The eutectic freezing temperature Is pressure had a slope of -0.9°Cper kbar. At 50 khars, the nickel-nickel carbide eutectic was at 1297° * 5°C and 0.34 mole fraction Ni3C. The composition of the eutectic increased at an initial rate of 0.004 mol fraction per kbar. The carbon content of the a phase also increased with pressure. Seveval illustrations of nickel carbide microstruc-tures are given and data on the lattice expansion of nickel in terms of carbon content are included. IRON, cobalt, and nickel form a variety of carbides with compositions varying between MeC and MC. Of the three, the carbides of iron are most easily recovered. The nickel carbides are so unstable at temperatures above 900°C that their occurrence in Ni-C alloys is unusual. Under sufficient pressure, however, the temperature range for the stability of the ferrous metal carbides is likely to be increased, or their decomposition suppressed (e.g., see Hilliard' on FesC), providing an opportunity to study the unstable carbides more closely. This was found to be true for nickel carbide which, under pressure, formed a eutectic with nickel. This paper describes the conditions of formation of nickel-nickel carbide eutectic compositions and their subsequent recovery. Despite the comparative instability of the nickel carbides, something is already known about them through various chemical reactions at temperatures not exceeding a few hundred degrees, and from their recovery by the very rapid quenching of molten Ni-C alloys from temperatures of about 1450°C or above. At least four carbides of nickel have been reported: A discussion of the state of knowledge about Ni3C is given by ansen.' The studies of Morrogh and williams7 who obtained Widmanstatten nickel carbide structures and of sidorenko8 who first obtained nickel carbide eutectic structures are also of interest. Sidorenko used short heating times for molten nickel in a graphite crucible followed by very rapid quenching to obtain the eutectic structures. Long heating times produced only the nickel-graphite eutectic probably due to the presence of graphite crystals in the melt which nucleated graphite crystallization. According to the early work summarized by anssen,' nickel carbide may form at temperatures far above the melting point and may be recovered by very rapid quenching. More recently, Giardini and Tydings, working on diamond synthesis, found evidence for "free nickel carbide'' in high-pressure reactions carried to temperatures far in excess of the limit for diamond growth, followed by rapid thermal quench. They stated that nickel carbide was not found in association with diamond growth. In the present work, observations were made on the melting and solidification temperatures of Ni-C alloys as a function of composition, temperature, and pressure. The nickel-nickel carbide eutectic was found at pressures above 10 kbar and its variation with pressure followed up to 60 kbar. Nickel-nickel carbide microstructures were recovered by quenching under pressure from temperatures of about 1400°C and higher. The formation of nickel carbide structures under ordinary diamond-growing conditions was usually observed but the role of carbide formation as an intermediate step in diamond growth needs more study. EXPERIMENTAL METHODS The melting and solidification temperatures of various nickel-graphite compositions were observed by latent-heat arrests in the sample holder illustrated in Fig. 1. The samples were composed of mixtures of carbonyl nickel powder and National Carbon Co.'s SP-1 graphite packed to densities of about 6.4 g per cu cm. They were contained within

Jan 1, 1965

By P. Pietrokowsky

lntermediate phases in the binary metal alloy systems Ti-Zn, Ti-Hg, Zr-Zn, Zr-Cd, and Zr-Hg have been investigated by X-ray powder diffraction methods. Gamma-TiBHg and Zr3Hg have a beta tungsten structure; TiHg and ZrHg are analogous to ordered AuCu (L l0 type); delta-TixHg and ZrHg, are isomorphous with ordered AuCu,, (L l2 type); ZrZnz is face-centered cubic (C 15 type); TiZna crystallizes in a C 14 type structure; and Zrll-, occurs in cubic and tetragonal modifications in which a random distribution of atoms exists. Additional information for the intermediate phase TiZn, is presented. THE physical metallurgy of titanium and zir-conium when alloyed with elements in subgroup 11-B of the periodic table has received comparatively little attention in the literature. Laves and Wallbaum' reported the existence of several intermediate phases in the system Ti-Zn. They identified TiZn as a CsCl (B 2) structure and described TiZn, as an ordered Cu,Au (L 1, type) crystal structure. Gebhardt' investigated very limited zinc-rich regions in the systems Ti-Zn and Zr-Zn. Phase relationships in these partial constitution diagrams were deduced from the results of thermal analysis and metallography, X-ray results being inconclusive. The first zinc-rich intermediate phase in either system was not identified. More recently, Anderson, Boyle, and Ramsey" have had occasion to refer to a partial Ti-Zn phase diagram (unpublished data) covering the region 0 to 10 atomic pct Ti, wherein two intermediate phases corresponding approximately to TiZn,, and TiZn,, were indicated. The metals used in this investigation and typical analyses as determined by the suppliers are given in Table I. The iodide-process zirconium which was used was not hafnium free. Experimental Methods Alloy Preparation: The relative ease with which titanium and zirconium combine with other elements places extensive restrictions on the methods by which alloying can be achieved. The direct current electric arc melting procedure was found to be unsatisfactory for preparing these binary alloys and for this reason solid state diffusion methods were utilized. The iodide process titanium and zirconium rods were filed by hand. Fines were subjected to a magnetic separation and classified as to size as either finer than 200 mesh or coarser than 200 but finer than 80 mesh. Powder mixtures of various binary combinations of titanium and zirconium with zinc and cadmium were compacted in a 12 mm diameter die and then placed in Vycor or quartz vials which were evacuated and sealed. The mercury alloys were prepared in a similar manner; the proper weight of liquid mercury being placed in a vial with minus 200 mesh titanium or zirconium. These ampoules were then heat treated at various temperatures and times depending on the characteristics of the particular alloy system. Upon completion of the heat treatment the ampoules were cooled rapidly and the specimens weighed. The loss in weight varied from 1 to 3 pct (except as noted in the text) and for this reason the calculated compositions were accepted as a fair measure of the actual alloy compositions. X-Ray Dif raction Techniques: Powder diffraction experiments were conducted at room temperature with a 143.2 mm Debye-Scherrer X-ray camera in which the film was placed in the Straumanis arrangement. When copper radiation was used, a nickel filter was employed, and for the cobalt target a filter of iron oxide was used. In both cases, the /i? filter was placed between the X-ray target and the powder specimen which was mounted on a glass fiber. The lack of information based on optical metallography placed reliance on the results obtained from the X-ray experiments for determination of

Jan 1, 1955

By G. A. Vissac

The only fine coal washer with proved automatic controls, the feldspar jig is capable of good efficiencies even at low separating gravities, handles a variety of products, and treats 150 tph and over. IN continental Europe the feldspar jig is used almost exclusively for cleaning the fine sizes of coal; it operates with an artificial bed, made up generally of pieces of feldspar or of any other hard and heavy rock with good cleavages. A primitive form of this machine requiring close supervision was used in this country years ago, but output was small. The modern machines are generally air-pulsated Baum-type jigs, with capacities up to 150 tph, and treat sizes from % in. to 0, usually previously dedusted or deslimed. These jigs are equipped with very accurate and sensitive automatic controls insuring satisfactory operation even at low separating gravity and with feeds irregular in quality and quantity. This paper will deal more particularly with coal cleaning separation, but the technical studies apply equally to all minerals. Theory of the Feldspar Jig To understand fully the operation of the feldspar jig and to appreciate its potential value, it is necessary to measure and analyze the motion of small particles of various specific gravities, falling in various media, under various conditions. As no practical formulas were available for that purpose, the writer has developed new theories and established new sets of formulas, which cannot be demonstrated here. They are applicable to all minerals and to many problems of coal or mineral concentration. These formulas do not pretend to absolute accuracy, but results, tested by comparison with experimentally recorded data, are sufficient for practical purposes, as they give definite indications of trends, relative values, and order of magnitude of the many factors involved. For pulsating motions no earlier formulas are available. In the case of continuous currents or motions, such formulas as Rittinger's, Allen's, or Stokes', over a hundred years old, apply only to special shapes and sizes of particles, involve factors and coefficients difficult to measure or appreciate, and deal only with free motions. They are of little use in solving practical problems. Units used with the formulas presented here are in the CGS system. Lateral friction and suction have been taken into account according- to methods currently used in aerodynamics, and only hindered motion is dealt with. As the feldspar jig is primarily intended to create a fluid bed condition, the mixture of fluids and solids obtained is homogeneous, and the apparent specific gravity of the separating medium is calculated accordingly. For instance, if 20 pct of the volume is coal and shale, with an average of 1.60 sp gr, in a liquid of 1.10 sp gr, the actual specific gravity of the separating fluid is 0.80 x 1.1 + 0.20 X 1.6 = 1.20. The fundamental equations are as follows: The general motion of a particle falling in a medium of specific gravity equal to u, hindered motion. is dv/dt = g/Ls [ L (s-u) - u/g v2 [1] g = 981 cm per sec, acceleration of gravity, and L = thickness of the particle of specific gravity (s) and velocity (v). The initial acceleration dv/dt = g (1-u/s ) [2] is a function of the specific gravity of the particle, only for a given medium, and independent of its dimensions—an ideal separating condition. The terminal velocity Vt = gxL- (s-u)/u, [3] for a given value of u, is a function of s and L. Two particles, L, s, and L2 s2, are said to be equivalent if they have the same terminal velocity, and accordingly L1/L2=s2-u/s1-u. [4] Two such particles cannot be separated by continuous currents, in any concentrating device. Because the initial accelerated motion, which provides for efficient separation, is followed by a constant velocity, which has a limiting effect, it is essen-

Jan 1, 1956

By Maurice Lacasse, Pierre Legast

GENERAL OUTLINE For more than one hundred years, asbestos ore has been mined on Les Mines d’Amiante Bell's property at Thetford-Mines , Quebec, Canada. In 1878, the first tons of fibre were produced. The mine operated as an open pit until 1951 at a yearly production of about 330 000 mt of ore. Since 1951, the mine has operated underground using a block caving method. The mine produced 725 000 mt per year until 1978, when the rate of production was increased to 1 100 000 mt. The ore was produced entirely fm the first lift on 650 level until 1976. Then, a second lift on 950 level was put into operation to replace production facilities fm the first lift which is now exhausted. Annual fibre production is 72 500 mt with grades £ran 3 to 7. The total work force is 600 people. The host rock is a peridotite partially serpentinized. The asbestos fibre seams occur as stockwork deposit structurally controlled by talcose shear zone. The geological rock formations are heavily jointed and have a wide range of competence. Asbestos ore bodies have an heterogeneous nature which des difficult geological interpretation. THE GRIZZLY METHODS A full gravity method was used on the first level where the caved ore was drawn from finger raises onto grizzly bars spaced at 480 mn. Oversize blocks were reduced by secondary blasting. The ore fell by gravity in- to the ore pass below the grizzly chamber and was loaded into 5.7 mt haulage cars through a 1.2 m wide chute. Access to the undercut drift was fm the grizzly drift through finger raises. The undercut trough was drilled and blasted in a 1.2 m interval ring sequence into a slot situated at the end of each panel. The undercut stope was emptied through the finger raises. The undercut retreated from South to North at blast interval determined by the finger raises spacing. Fig. 1 represents the various steps involved with the grizzly method. Extraction drift dimensions were opened 1.8 m wide x 2.4 m high with anchor rock bolts and wire mesh where safety required them during excavation. Grizzly chambers were excavated at 2.4 x 2.4 x 4.6 m long on a 7.6 x 7.6 m grid spacing. Ore passes with dimensions of 1.5 x 1.5 m were developed from the haulage drift. On the extraction level, headings were drilled with jacklegs and cleaned by slusher into ore passes to the haulage chutes. The support used in the grizzly chambers was square concrete structure with 150 mn H beam reinforcement. The H beam was partially buried in the concrete and had one free face to allow for difference frequency of blast vibration between concrete and steel. The supported brow of the chamber had an opening 1.5 x 2.1 m. Ore passes were ring concreted 150 mn thick without any reinforcement. A 24 MPa compressive strength concrete was pumped and poured in pre-assembled forms. Based on the success of this method on the first level, the same layout was repeated on the second level. With the start of undercutting on the second lift, signs of deterioration were noticed in extraction drifts. At first, there was great concern as the operators were confident that standard repair techniques could cope with such a situation. An intensive program of support repair and a reduction of draw resulted. The following method of repairs were used: 1) Steel square sets of 150 mn H beam at 0.6 m intervals were installed. 2) This was reduced later to 0.3 m interval and eventually to a skin to skin steel structure. 3) Yieldable arches were introduced spaced at 0.9 m intervals, linked laterally with 150 m. H beam. 4) The yieldable arches spacing was then reduced to 0.46 m and eventually installed skin to skin. However, this support was not successful.

Jan 1, 1981

By Sidney G. Parker, Jack E. Pinnell

Cubic ZnSe crystals have been grown with HCl, HBr, and I, as chemical transport reagents. The growth of large, well faceted crystals is in the order HCl < HBr < I, with some produced by I, transport being 1 cm on an edge. ZnSe:I crystals showed no strain in cross polarized light and were homogeneous as determined by electron microprobe. These ZnSe:I crystals had a mobility at 25°C of about 300 sq cm per v-sec and contained 103 dislocations per sq cm; further, these crystals were pure cubic and showed both photolumi-nescence and photo conductance. Doping was attempted during crystal growth. ZnS and Zn (S,Se) crystals were also grown by I, transport. ZnSe crystals have been grown by most of the common techniques.1"6 Of these, chemical vapor transport as developed by Kaldis2 showed promise of producing high perfection, cubic ZnSe. With chemical transport, crystals can be grown far below the transition temperature for conversion of cubic to hexagonal structure. A small temperature gradient between source and growth region tends to allow near equilibrium growth, which should lead to good crystalline perfection. Because it is necessary to form volatile compounds, halogens or their compounds are extensively used as transport agents. HCl, HBr, and I, were compared as transport agents for growth of ZnSe crystals. Doping during crystal growth was attempted. ZnS and ZnSxSe1-x crystals were also grown by chemical transport. Electrical and optical properties of the crystals were examined. EXPERIMENTAL Fig. 1 is a sketch of the growth apparatus, which was a modification of Kaldis&apos;. A quartz rod which butted against the seed crystal served as a heat sink to promote growth only on the seed. Initially, crystal growth was attempted with ZnSe prepared by wet chemical methods. Because such a material contained oxides and selenates, HC1 reacted with these oxygen compounds to form H2O and no ZnSe transport occurred. Further, this ZnSe contained about 10 ppm Cu plus other impurities. High purity ZnSe, containing small amounts or no oxygen compounds, was prepared by reaction of H2Se with zinc vapors at 600° to 800°C in an atmosphere of palladium diffused H2.7 The ZnSe thus produced was usually copper free and contained only 1 ppm by weight of magnesium as determined by emission spectrographic analysis. G.E.&apos;s electronic grade ZnS, which had about 10 ppm metallic impurities, was used without further treatment. ZnS-ZnSe charges were prepared by mixing the two compounds together, then sintering 24 hr at 1100°C in an H2S ambient. The gases, HBr and HC1, were commercial grade, of 99.9 pct purity, while the I2 was 99.999 pct pure. The single crystal seeds with (111) faces for growth were mechanically held in place by sealing the outer quartz tube to the growth tube. After the charge was introduced, the system was outgassed at l0-5 torr while heated to 500°C. The desired quantities of transport reagents were then sealed off in the system, which had been cooled to 25°C. The growth tubes were inserted into a furnace with the desired temperature and thermal gradient. The system was allowed to cool for 1 to 12 hr from growth temperatures of about 850" to 25°C. The tubes remained stationary during crystal growth. HCl CHEMICAL TRANSPORT GROWTH Preliminary runs with HC1 had a temperature gradient of 100° to 200°C and no seed or heat sink. Only small crystals were obtained in these experiments as

Jan 1, 1970

By J. F. Butler

Boron nitride, BN, has been identified in boron low-carbon steels by means of light microscopy, electron microscopy and diffraction, and chemical analysis. This boron nitride is responsible for strain aging suppression in these steels through the removal of nitrogen from solution; however, small oxidizing potentials which result in deboronization In the austenitic temperature range also result in boron nitride decomposition and the subsequent occurrence of nitrogen strain aging. THE addition of boron to low-carbon steels is an effective means of eliminating the detrimental effects of strain aging;&apos;,&apos; however, the mechanism by which boron suppresses strain aging has not been established. In studying the effect of heat treatment on the strain aging of boron low-carbon steels, Butler3 found that no detectable nitrogen was present in the ferrite solid solution after various heat treatments even though the total nitrogen analyses of the steels were 0.003 pct N. Apparently the function of boron in suppressing strain aging is the removal of nitrogen from solution to form a relatively stable second phase. A clue to the identity of this phase was found by Speight4 who extracted from an aluminum-killed boron steel an acid insoluble residue which contained boron and nitrogen in proportions corresponding to the compound, BN. Shyne and Morgan5 found that the addition of nitrogen to a hardenable boron steel lowered its hardenability in a manner which suggest-d the presence of nucleating particles (presumably BN) even at high austenitizing temperatures. Although this indirect evidence for the presence of boron nitride in boron steels has been found, the compound was not identified metallographically as a separate phase in these steels. Because boron has an affinity for oxygen comparable to that of silicon,5 boron steels must be thoroughly killed with aluminum in order to prevent the reaction of boron with oxygen.7 The affinity of boron for oxygen also is demonstrated through the ease of deboronization of a boron steel in an oxidizing atmosphere. Digges, Irish, and Carwile8 found that a mixture of wet natural gas and air caused both deboronixation and decarburization of a boron steel at 1900°F. The boron content rose at the surface of the steel due to the formation of boron oxide. Shyne and Morgan9 encountered deboronization at much lower oxygen potentials; loss of boron occurred in steels treated at 1750o F under argon purified to 0.0014 pct 0, even though decarburization did not occur. Boron oxide, B2O3, is much more stable than the nitride, BN, as is indicated by the standard free energies of formation at 980oC: -235 kcal per mol of B2O3 (liquid) and -28 kcal per mol of BN (crystal). It is evident that the oxygen potential must be kept low in the presence of BN in order to prevent its decomposition and the subsequent formation of B2O3&apos; The purpose of the work described in this paper was to identify the nitride phase responsible for the removal of nitrogen from solution and to study its stability under oxidizing conditions. IDENTIFICATION OF BN In order to identify the phase containing boron and nitrogen, several alloys high in boron and nitrogen were made up in a small vacuum furnace. In alloys 3 and 4, Table I, electrolytic iron was used as a charge material. Boron additions were made in the form of 18 pct B ferro-boron after the iron was molten. In the case of alloy 3, the charge was solidified at this point; for alloy 4, nitrogen at 1 atm pressure was admitted over the melt before it was

Jan 1, 1962

By David A. Sterling, Roger C. Malan

The Atomic Energy Commission is investigating the distribution of uranium and thorium in the Precambrian of the western United States and the relationship of time-space-facies patterns of uranium and thorium enrichment in the Precambrian, to the major resources of umanium in Mesozoic and Cenozoic continental clastic sediments. The results of preliminary studies in the southwestern. United States are summarized. Approximately 50% of the uranium resource of the Free World is in deposits of Precambrian age, principally in lower Proterozoic conglomerates in Canada and South Africa (Uranium Resources, Joint Report, ENEA and IAEA, 1967). Most of the uranium resource of the United States is in Mesozoic and Cenozoic continental clastic sedimentary rocks that fill intracratonic basins. The Atomic Energy Commission (AEC) is investigating the distribution of uranium and thorium in the Precambrian of the western United States and the relationship of time-space-facies patterns of uranium and thorium enrichment in the Precambrian to the major resources of uranium in the Mesozoic and Ce-nozoic host sedimentary rocks. This paper summarizes the results of preliminary studies of the Precambrian in the southwestern United States including New Mexico, Arizona, southern Nevada, and southern California (Fig. 1). The host rock provenances for the major uranium resources in epigenetic deposits of Mesozoic and Ce-nozoic age in the western United States were in areas of extensive Precambrian exposure along the eastern margin of the Phanerozoic geosynclinal belt (Fig. 2). Mesozoic continental clastic sediments in the Colorado Plateau contain about two-thirds of the uranium resource of the United States. These sediments formed from detritus derived from the Mogollon highland in the southwestern United States where the Precambrian was extensively exposed1-1 (Fig. 2). A genetic relationship may exist between this provenance and the major uranium deposits of the Colorado Plateau. The Pre- cambrian might be equally important in the genesis of uranium deposits whether the most important process in the formation of these deposits was the leaching of low-order intrinsic amounts of uranium from Precam-brian granite or from Mesozoic pyroclastics derived from syntexis of the Precambrian basement rocks.&apos; Precambrian Geochronology of the Southwestern United States The Precambrian geochronology of the southwestern United States is in an early stage of systematic study. Until recently, the only basis of correlation was through inconclusive field relationships. However, with the increased use of isotopic age dating, new data are becoming available for correlating regional and local events. As yet, there is no undisputed evidence of ages greater than 1.8 billion years (by) old in the southwestern United States. However, most geologists who have studied the region agree that volcanism and marine sedimentation of predominately eugeosynclinal facies took place in a northeasterly trending geosyn-cline prior to 1.7 by."&apos; Because of insufficient evidence for a pregeosynclinal continental crust, some researchers believe the geosyncline may have developed on oceanic crust.&apos; However, sediments metamorphosed to 1.7 by-old felsic paragneisses in the Panamint Range, California," and southeastward into southern Nevada are believed to have had a nearby continental provenance. The three Precambrian disturbances that are recognized in the southwestern United States are 1.6 to 1.8 by, about 1.4 by, and about 1.1 by-old (Fig. 3). In addition to plutonism, these disturbances are characterized by predominately lower-grade metamorphism. In this report, lower-grade metamorphic rocks include argillite, phyllite, slate, mica schist, and gneiss with relic sedimentary textures. Higher-grade metamorphic rocks, in this report, are recrystallized beyond megascopic recognition of the original rock type. Principal

Jan 1, 1971

By W. C. Winegard, W. J. Bratina

Internal friction characteristics and temperature dependence of the torsion modulus for iodide zirconium containing 2.4 pct Hf were investigated, using a low frequency pendulum technique. The internal friction curve consists of a background which increases as the temperature increases, a maximum at 860°C apparently a background due to the al-lotropic transformation, a maximum due to grain boundary relaxation with an associated heat of activation of 58,000 cal per mol, and an anomaly below 350°C which may be associated with a precipitation perphenomenon, Oxygen in below small amounts reduces the grain boundary maximum substantially. The variation of the torsion modulus at 20°C was found to be 3450 Kg per mm2 for the zirconium used in the present work. IT is well known that small amounts of certain solutes materially affect the ductility of zirconium. Lely and Hamburger,&apos; as early as 1914, found that high purity zirconium exhibited a remarkable ductility, while Fast&apos; has shown that oxygen and nitrogen can cause substantia1 embrittlement. Treco" has recently demonstrated that the ductility decreases sharply with the oxygen content, and that 2 atomic pct O2 embrittles zirconium to such an extent that cold working is impossible. The marked decrease in ductility is difficult to understand in view of the fact that Domagala and McPherson4 report the solid solubility of oxygen in zirconium to be 29 atomic pct at 500 °C. Another metal which behaves much the same as zirconium in this respect is titanium. Pratt et al." investigated the internal friction characteristics of titanium and the effect of oxygen on the internal friction values. It is evident that internal friction measurements are of value for studying grain boundary segregation, as shown by Pratt et al. for oxygen in titanium, by Pearson for oxygen in copper, and by Maringer and Schwope for oxygen in molybdenum. With this in view, the internal friction characteristics of zirconium and the qualitative effect of oxygen on the grain boundary relaxation phenomenon were investigated. Materials and Experimental Procedure The zirconium used in the present work was supplied by the Foote Mineral Co. in the form of wire 0.05 in. diam. The analysis supplied by the manufacturer indicates the amount of hafnium as 2.4 pct, less than 0.01 pct O less than 0.01 pct N,, less than 0.02 pct H,, and less than 0.001 pct C. Additional spectro-graphic analysis indicates the other main impurities as follows: 0.01 pct Fe, 0.05 pct Si, 0.008 pct Cu, <0.005 pct W, <0.001 pct Al, <0.05 pct Mg, <0.001 pct Ni, <0.02 pct Ca, and <0.01 pct Ti. Microscopic examination of the material in the as received condition revealed very fine grains with numerous twins. Specimens were annealed either in situ in the internal friction apparatus or in evacuated silica tubes in an auxiliary furnace. When the specimens were annealed in the auxiliary furnace, they were wrapped in identical zirconium wire to prevent contamination by the container. Metallographic sections were taken in all cases. Some were taken from the specimens used for internal friction measurements after completion of the experiments, while others were taken from control specimens at intermediate stages of the experiments. lnternal friction values were obtained by measuring the free decay of a low frequency torsion pendulum (1 cycle per sec), the suspension of which was

Jan 1, 1957

By F. D. Rosi, C. A. Dube, B. H. Alexander

WHEN a deformed polpcrystalline metal is heated to a sufficiently high temperature, a recrystallized structure develops which consists of small, essentially stress-free grains. This transformation is referred to as primary recrystallization. Under certain conditions, on prolonged annealing of the specimens, a type of grain coarsening occurs in which a small number of grains commence to grow at various points by devouring the neighboring finegrained primary structure, which, in itself, exhibits a marked stability toward normal grain growth. This grain coarsening process has been referred to by Burgers&apos; as "secondary recrystallization" or "exaggerated grain growth." Although much work has been done on recrystallization and growth processes, present knowledge of the factors which determine the occurrence and growth of secondary grains is inadequate for the advancement of a theory which accounts for the observed characteristics of this recrystallization phenomenon. In this respect, it would be important to make measurements of the velocity of growth of these large secondary grains. The early work of Feitnecht2 on aluminum showed that the size of secondary grains increased with temperature and time, suggesting that such measurements would be possible. More recently, Burgers1 found that the growth velocity of these grains in aluminum was constant over a large time interval, as is generally found for the growth velocity of primary grains in a uniformly deformed test piece.3-5 It is reasonable to expect that the determination of the activation energy of the secondary growth process might lead to a better understanding of the underlying atomic mechanism. This investigation, therefore, is one of a series primarily designed to measure the growth velocity of secondary grains at various temperatures for silver, copper, and aluminum. It is hoped that these studies along with those of orientation relationships, will establish a sound basis for theorizing as to the origin and nature of the secondary transformation. Experimental Procedure The metal used in the present investigation was high-purity silver (999.9 fine), which was supplied in the form of cold-rolled plates 0.250 in. thick. These plates were annealed at 500°C for 1 hr and then straight-rolled to a thickness of 0.04 in. in three reductions of approximately 45 pct, followed in each case by an anneal at 450°C for 1/2 hr. The 0.04 in. sheets were given a final reduction of approximately 50 pct, which resulted in a thickness of 0.02 in., thereby insuring two-dimensional crystal growth. Individual specimens of this material about 1x3 cm were used for all heat treatments, unless otherwise noted. The annealing was carried out under an atmosphere of argon in an Inconel tube furnace whose temperature was controlled to within -+2°C. Metallographic examination of the secondary transformation was accomplished by mechanically polishing the specimens on one side to approximately one half their thickness through 2/0 metallographic emery paper, and then electrolytically polishing in a solution of potassium ferrocyanide and sodium cyanide. With a current density of approximately 20 amp per sq dm, the time required to obtain a satisfactory surface varied from 3 to 5 min. Standard potassium bichromate was used to etch the electrolytically polished surfaces. A heavy etch with this solution produced a sharp contrast between the secondary grains and the fine-grained primary structure, darkening the latter while leaving the large secondary grains bright. All area measurements of the secondary crystals were made with a planimeter on enlarged tracings of the grains.

Jan 1, 1953

By Harold L. Overton, Leonard B. Lipson

The first paper in this series1 outlined practical methods for applying the theory of steady-state flow of an ideal Bingham plastic liquid through a circular pipe and axially through a stationary concentric annulus to the enginekring analysis of friction loss problems. In the present paper the properties of another useful rheological model, the pseudoplastic generalized Newtonian liquid, are considered. The terminology applied to the rheological models is derived from the following classification of rheological models. The term "generalized Newtonian" is a class designation applied to models which do not have yield points but which exhibit a dependence on shear rate. The term "pseudoplastic" applies to a sub-group of models within this class which exhibit a decrease in "viscosity" with increasing shear rate. The term "power model" refers to a mathematical model proposed for describing the behavior of the pseudoplastic liquid. This model is of interest since certain of the salt saturated, oil emulsion, and "low solids" drilling fluids, inverted emulsion- and oil-base drilling fluids, aqueous gels, gelled crudes and blocking agents employed in hydraulic fracturing operations are of this type. The present treatment considers the equations describing steady-state Poiseuille flow through a circular pipe and a stationary concentric annul us, and Couette flow between concentric rotating cylinders for a particular pseudoplastic model. As in the previous paper&apos; it is demonstrated how these equations can be applied to engineering calculations of friction losses. Graphical procedures for recovering the various flow curves and cxample calculations are included. A method for simplifying turbulent-flow correlations is also proposed. PROPERTIES OF PSEUDOPLASTIC GENERALIZED NEWTONIAN LIQUID In contrast to the Bingham plastic the generalized Newtonian liquid is yield point-free. However, in the flow region the relation between stress and rate of shear is not linear as it is with ordinary Newtonian fluids. If the stress increases with shear rate at a less than linear rate the system is called pseudoplastic. While there is no yield point in this system, the Bingham advocates&apos; coined the term pseudoplastic to distinguish this kind of behavior from Bingham plastic behavior. For the pseudoplastic a plot of flow rate vs friction loss or rpm vs torque, from pipe flow or rotational viscometer measurements, respectively, generally has three qualities: (1) it can be clearly extrapolated toward the origin; (2) there is very little slope at the origin. This accounts for the high apparent viscosities at low mixing and pumping rates; and (3) the flow curve possesses a continuous curvature which gradually diminishes as the shear increases. Rheological measurements on a pseudoplastic liquid can be easily misinterpreted as indicating Bingham plastic behavior. A typical case in point is illustrated in Fig. 1. These data were obtained from measurements on an oil-emulsion mud using a commercially available rotational-type viscometer (Model 35 Fann V-G meter). Applying the "two-point"* method3 gives a plastic viscosity of 17 cp and a yield point of 24 lb/100 ft2; at the same time weighting material settles very easily in this system. This illustrates that it is not possible to distinguish between the pseudoplastic and the Bingham plastic from only two data points. It is possible to determine qualitatively which model is more appropriate by a combination of dynamic and static measurements. Experience indicates that the simplest criterion for the Bingham plastic liquid is that the calculated dynamic yield point should be of the same magnitude as the measured gel strengths. For the oil-emulsion drilling fluid illustrated in Fig. 1, a value of 4 lb/100 ft2 was obtained for gel strengths measured

By James E. Lawver, James L. Wright

This paper describes the design of a cell used to measure the electrical conductivity, or the reciprocal resistivity, of granular materials. It also establishes a quantitative relationship between the electrical conductivity and the electrical separation of selected mineral samples. It is estimated&apos; that the free world produces about 13 million tons of mineral concentrates a year by electrostatic or electrodynamic methods. At least 95% of these concentrates are produced by corona discharge type machines that separate minerals by exploiting the differences in their electrical conductivity. But, what is meant by the electrical conductivity of a mineral? How large a difference in the electrical conductivity of two mineral species is necessary to effect a separation? Just what is the role of conductivity in electrical separations with regard to capacity and selectivity? There is a considerable amount of information in the literature on both the mechanisms of conduction and the values of the electrical conductivity of pure single-crystal mineral specimens. In addition, some insight into the role of mineral conductivity can be obtained by referring to a Bureau of Mines publication&apos; in which 95 minerals have been grouped as conductors or insulators as a function of temperature. The classification was made on the basis of the percent of weight that reported as "conductors" in an electrical separator. But, as is often the case in the mineral industry, practical application leads theory — and there is little useful information in the literature giving any kind of quantitative relationship between electrical conductivity and electrical separations. The problem is a bit complex because electrical conductivity per se — which can be rather easily measured on large, single grains — is not sufficiently informative to permit quantitative predictions of the separability of the mineral system. Practical "high-tension"* separations are made at such feed rates that the band of minerals on the rotor is multilayered in thickness. Thus, the effective conductivities of minerals as seen by a high-tension machine include particle-to-particle contact resistance, which is often a controlling factor in making a separation. This is particularly true when the mineral grains are coated with slime or with a dielectric surface film. From a high-tension separation viewpoint, one is actually concerned with the time required for corona-charged grains to lose enough charge so that the centrifugal force acting on the particles exceeds the image force holding the grains to the rotor. This calculation requires a knowledge of the effective mineral conductivity s. (The conductivity of the metal rotor is sufficiently greater than that of the minerals so that it need not be considered in charge decay calculations.) The charge density at time t can be approximated by the relaxation equation.3 where t 5 charge density at time t r, - charge density when t = 0 cr e total electrical conductivity £ = permittivity The time required for the charge density to fall to l/e of its initial value is called the relaxation time and is numerically equal to €/n. AS defined here, u is the conductivity of an element of homogeneous grains making contact with each other and with a grounded rotor. This paper deals with the design of a conductivity cell used to measure a, or its reciprocal p, the electrical resistivity. CELL DESIGN Initial test work was performed with a cell recommended by ASTM.4 Since the reproducibility with the ASTM cell was not satisfactory, it was decided to

Jan 1, 1970

By R. J. Schaefer, M. E. Glicksman

Direct, in situ observation of metallic alloys during solidification reveals that in some systems crystal multiplication occurs by means of a dendrite remelt-ing process, without the necessity of independent nu-cleation events. The solidification is observed on optically clean surfaces of supercooled molten alloys. In one system (Sn-3 wt pct Bi) , a fine-grained equi-axed structure is produced by the complete disintegration, via remelting, of transient initial dendrites. In contrast, several other metallic systems show little or no evidence of remelting activity. The behavior of these metallic systems is consistent with that expected on the basis of published observations of dendrite remelting in transparent organic alloy systems. It is concluded that dendrite remelting is an important crystal multiplication process in some metallic alloys, but is velatively unimportant in some other alloys. The detachment of dendrite branches from the primary stem by a remelting process has been observed by Jackson, Hunt, Uhlmann, and seward1 during the solidification of some transparent organic alloy systems. The branches released by this remelting process can drift free of the primary stem and serve as seeds for the formation of numerous independent crystals. This proliferation of new crystals does not require repeated independent nucleation events, but only modification of the initial solidification structure. The mechanism of dendrite remelting, as described by Jackson et a1.1 and by Tiller and O&apos;&apos;Hara,2 is dependent on the transport of both heat and solute and is, therefore, expected to operate only in alloys, and not in pure substances. It was found in the transparent organic alloy systems that remelting occurred primarily in the constricted regions near the base of dendrite branches, where the branches had grown through the solute-rich liquid layer surrounding the primary dendrite stem. It was suggested that impure solid had formed in these constricted regions at a relatively low temperature and had later become unstable as further solidification of purer material raised the temperature. Jackson et al. proposed that the equiaxed zone of metal alloy castings originates from a similar remelting process, and they demonstrated the operation of this mechanism in "ingots" poured from saturated salt solutions. Although these substances were especially selected to show solidification behavior similar to that of metals,3 the remelting mechanism has, until now, been subject to the objection that its operation has not been directly observed in a metallic system. Considering the fact that thermal properties such as diffusivity may differ by as much as two or three orders of magnitude between metals and organic compounds, this objection was considered to be possibly serious. A method has now been developed by which it is possible to make direct optical observations of metals during solidification. This method has revealed transient solidification processes which would not be detected by metallographic examination of totally solidified specimens. In particular, a grain-refinement process in a metallic alloy has been observed to be a direct consequence of the total disintegration of an initial dendritic structure. The influence of an initial, transient solidification structure on the final solidification structure is demonstrated here for the first time in a metallic system. I) EXPERIMENTAL The technique of using a transparent flux to maintain an optically clean metal surface during solidification has been described by us elsewhere.* The

Jan 1, 1968

By Robert Hoy

If the reader finds that the basic information in a commodity chapter is insufficient, he can consult the appropriate sources in this chapter to find more detailed or more up-to-date information. In these days, technology develops so rapidly that this 4th edition will be somewhat out of date even by the time it is distributed. A comparison of this edition with the 3rd edition (1960) of Industrial Minerals and Rocks will clearly demonstrate how rapidly the scene changes. One of the best sources of new information, of course, is attendance at technical meetings. For example, the papers presented at the national and sectional meetings of AIME usually discuss new developments in the respective divisions of the society. Frequently this information is available in Preprints. In addition some are printed in Mining Engineering and/or the Transactions of the Society of Mining Engineers of AIME. Furthermore, other professional and trade journals contain articles pertinent to the field. A journal introduced in 1967, Industrial Minerals, published by the Metal Bulletin, Ltd., London, is an excellent source of information. The Mining Journal, Ltd., also in London, publishes a weekly journal, a Mining Magazine (monthly), and a Mining Annual Re- view. The latter covers the field from three aspects: (1) by commodities, (2) through technical developments, and (3) geographically. Other useful magazines and periodicals include Engineering and Mining Journal, Pit and Quarry, Rock Products, and World Mining, all published in the United States. In addition many new books related to industrial minerals have been published since the 3rd edition of Industrial Minerals and Rocks. Most of these, of course, are included in the bibliography of each chapter in this volume. Another excellent information source is the proceedings of the Forum on Geology of Industrial Minerals. This group, which held its 11th annual meeting in 1975, is sponsored by a state geological survey or another mineral agency on a rotational basis. The proceedings have been published by the various sponsors and are available as indicated in Table 1. Two major sources of basic industrial mineral and rock data in the United States, and also a good source for many foreign countries, are the U.S. Geological Survey and the U.S. Bureau of Mines. The two agencies publish many reports and maps on a variety of geo- logical and mining subjects. In addition, each agency has an indexed list of all their publications with a free service announcing new publications. (New Publications of the Geological Survey, U.S. Geological Survey, Washington, D.C. 20242) and New Publications-Bureau of Mines, Publications Distribution Branch, U.S. Bureau of Mines, 4800 Forbes Ave., Pittsburgh, Pa. 15213). The U.S. Bureau of Mines (USBM) publishes annually Minerals Yearbooks which provide statistical data on mineral products including production, consumption, imports and exports, as well as information on new developments. Another very useful USBM series is called Mineral Facts and Problems. Editions were published in 1960, 1965, and 1970. Three other major series of publications by the Bureau are Information Circulars, Reports of Investigations, and Mineral Trade Notes. The latter is particularly good for news of foreign developments. A new Professional Paper No. 820 of the U.S. Geological Survey, 1973, summarizes data on the mineral resources of the entire country. The USGS, in cooperation with USBM, other Federal and various state agencies, has also prepared summary reports on mineral and water resources of given areas which include

Jan 1, 1975