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By Thomas L. Garrard, James A. Sprague, Rex B. McLellan, Samuel J. Horowitz

A simple rnodel for interstitial solid solutions has been devised in which each solute atom interacts with the solzlent lattice in such a way as to exclude an integral number of nearest-neighbor sites from being occupied by solute atoms. The vemaining interstitial sites ave not affected. In calculating the entropy of such a solution the increase in the number of interstitial sites available to solute atoms due to the ozlerlap of blocked sites is taken into account. The ther-modynamic functions and the solute activity fov the solution rnodel are calculated. It is shown that considevation of the overlap sues vise to a correction term of the order 8' ( where 0 is the ratio of solute to solvent atoms) in the thevmodynamic functions of the solution and the solute activity. The theo,uetical equation for the solute activity was used to analyze the available data for the activity of carbon in austenite at three different temperatures. The use of a computer enabled many comparisons to be made between the experimental activity data and those predicted by both the complex blocking model and the simple, widely used blocking model in which the ozierlapping of blocked sites is not taken into consideration. Even though at the highest concentvations oj carbon the value of 0 is small it is shown that the best fit to the experimental data is found with the complex blocking model. RECENTLY it has been shown by analysis of gas-solid equilibriums that many interstitial solid solutions can be described by the quasi-regular solution model in which the partial energy of solution E, is independent of composition and, apart from a composition-independent term due to nonconfigurational factors, the partial entropy is that of an ideal solution. Dilute solutions of nitrogen in both bcc and fcc iron,' dilute solutions of oxygen and silver,' carbon in a Fe,' and dilute solutions of carbon in ? Fe2 are all quasi-regular. In addition many hydrogen-metal solutions, both dilute and concentrated (with the notable exceptions of the H-Ni and H-Pd systems), can be described by this model.3 However, it has been shown that, at various temperatures, solutions of carbon in ? Fe begin to depart strongly from quasi-regular behavior at low concentrations. A plot of the activity of carbon in ? Fe relative to pure graphite vs atom fraction of carbon (Cc) calculated from Smith's data4 begins to depart from the (nonlinear) plot for a quasi-regular solution at about Cc = 0.02. Several statistical models have been proposed to account for the thermodynamic behavior of carbon in y Fe. Darken and smith4 set up a model in which a carbon atom in its octahedral site in the fcc lattice has either one or no neighboring carbon atoms in the twelve nearest-neighbor octahedral sites. It is assumed that the number of carbon atoms having more than one nearest neighbor is negligibly small and that a solute atom does not interact with another solute atom located at a greater distance than the first shell of interstitial sites. Thus this model contains two characteristic interaction energies. Darken and Smith showed that this model gives reasonable agreement with the measured variation of carbon activity ac with composition. It is noteworthy that Darken and Smith concluded from their analysis of the activity data using this model that there was a repulsive force between carbon atoms in austenite which reduces the concentration of C-C pairs below that corresponding to random mixing. Recently Aaronson, Domian, and pound5 have considered in detail the statistical model developed by Lachere and by Fowler and Guggenheim7 and have shown that it is compatible with the activity data for carbon in austenite. In Darken's model the energy of solution of carbon in austenite is dependent on temperature and concentration; the departure from Henry's law arises from the concentration dependence of the energy of solution. In Aaronson, Domian, and Pound's discussion of the Lacher, Fowler, Guggenheim model the interaction energy wy between adjacent carbon atoms in austenite is strongly temperature-dependent. Aaronson et al . suggested that this temperature dependence of wy and hence the energy of solution of carbon could be explained either by the formation of clusters of carbon atoms (despite the repulsive nature of wy) or by the dual occupancy of the octahedral and tetrahedral sites by the carbon atoms. However, a temperature-dependent heat of solution

Jan 1, 1968

By E. T. Turkdogan, J. H. Swisher

bi the fivst part of the paper results ave given on the rate of decarburization of Fe-C melts ln CO2-CO atmospheres at 1580°C. The rate -controlling step is believed to he that irvlloluing dissociation of curbotz dioxide on the suvfuce of the melt. 4 genevral reaction mechanistm is poslnlated jor gels-t11eta1 veactions oc-curit~g on the surface of iron coutcotamncited with chemi-sovbed osygesL. Oxygen the present work on decavbuvization of liquid iron and previous studies on the kinetics of nitrogen absorption and desorplion are discussed in terms of the postulated mechanism, ManY of the early studies of rate of decarburization of liquid steel were of an exploratory nature and laboratory exppriments carried out pertained to open-hearth or oxygen steelmaking processes. References to previous work on this subject may be found in a literature survey made by Ward. Using more sophisticated experimental techniques, several investigators have recently studied the kinetics of decarburization of molten Fe-C alloys in oxygen-bearing gases. For example, Baker et al2.' reported their findings on the rate of decarburization of liquid iron, levitated by an electromagnetic field, in carbon dioxide-carbon monoxide-helium atmospheres. In these levitation experiments the samples used were small in size, e.g., -0.6-cm-diam spheres weighing -0.7 g, and the rates were measured for decarburization from about 5 to 1 pct C at 1660°C. The rates obtained under their experimental conditions were considered to be controlled primarily by gaseous diffusion through the boundary layer at the surface of the levitated melt. Parlee and coworkers3 measured the rate of absorption of carbon monoxide in liquid iron. The rates were found to follow first-order reaction kinetics, yielding a reaction velocity or a mass transfer coefficient in the range 0.2 to 0.4 cm per min. The coefficient was found to decrease with increasing carbon content of the melt. These investigators attributed the observed rates to the transfer of carbon or oxygen through the diffusion boundary layer adjacent to the surface of the melt. In the work to be reported in this paper, an attempt has been made to study the kinetics of gas-metal surface reactions involved in the decarburization of liquid iron. EXPERIMENTAL The experiments consisted of melting 80-g samples from an Fe-1 pct C master alloy in an induction furnace and decarburizing in controlled CO2-CO mixtures at 1 atm pressure and 1580°C. The master alloy was prepared by adding graphite to electrolytic "Plastiron" melted in racuo. None of the impurities in the master alloy exceeded 0.005 pct. The reacting gases were dried by passage through columns of anhydrone; in addition, CO2 impurity in carbon monoxide was removed by passage through a column of ascarite. A schematic diagram of the apparatus is shown in Fig. 1. A 1.25-in.-diam recrys-tallized alumina crucible containing the sample was placed inside a 3-in.-diam quartz reaction tube, all of which was surrounded by an induction coil. A 450-kcps induction generator was used as the power source. Water-cooled brass flanges, which contained the gas inlet, gas exit, and sight port, were sealed to the top of the reaction tube with epoxy resin. The reacting gases were metered with capillary flowmeters and passed through a platinum wire-wound alumina preheating tube, 0.25 in. ID and 11 in. long. The gases were preheated to about 1300°C. A disappearing-filament optical pyrometer was used to measure the melt temperature. The pyrometer was initially calibrated against a Pt-6 pct Rh/Pt-30 pct Rh thermocouple. The temperature was controlled to within +10°C by manually adjusting the power input to the induction coil. In a typical experiment, an 80-g sample of the master alloy was melted in a CO2-CO atmosphere having pcO2/pco = 0.02 and flowing at 1 liter per min. A negligible amount of carbon was lost and no significant reduction of alumina from the crucible occurred during melting, e.g., 0.005 pct Al in the metal. After reaching the experimental temperature of 1580°C, the gas composition was changed to that desired for a particular series of decarburization experiments. The duration of the transient period for obtaining the desired gas composition at the surface of the melt was about 20 sec . The flow rate of the reacting gas was maintained at 1 liter per min. After a predetermined reaction time, the power to the furnace was turned off. During freezing, which took about 10 sec, the amount of gas evolution was not sufficient to result in a significant loss of carbon. The samples were analyzed for carbon by combustion and in a few cases they were analyzed for oxygen by the vacuum-fusion method. RESULTS A marked increase in the rate of decarburization of iron with increasing pcO2/pco ratio in the gas stream is demonstrated by the experimental results given in Figs. 2 and 3 for pco2/pco ratios from 0.033 to 4.0. In one series of experiments, denoted by filled triangles in Fig. 2, the reacting gas was diluted with argon (48 vol pct) resulting in a slower rate of decarburization. Samples from two series of experiments with pco2/pco = 0.033 and pco2/pco = 0.10 (with argon dilufion) were analyzed for oxygen. In these Samples the oxygen content increased with reaction time

Jan 1, 1968

By W. H. Yarroll

This paper presents a general discussion of the utility of the statistical technique known as multiple correlation, and gives three specific examples of its application. The first demonstrates the most simple form, or straight-line, multiple correlation. The other two demonstrate multiple correlation analysis in best-fitting third-degree parabolas. With the increasing availability of digital computers, the method becomes entirely feasible where heretofore its use was impractical. The advantages of the method are discussed, and curves are presented which were developed by computerizing the regression equations developed in the examples. The method described in this paper is for use with complex systems, and the examples given are complex metallurgical systems. This subject falls under the general classification of cybernetics, which is defined' as "the science of control and communication, in the animal and the machine." Machine, in this case, can include chemical and physical processes which take place within machines and processing equipment of all kinds. The classical approach to scientific investigation has been the construction of simple models and the changing of variables one at a time. This method is wholly inadequate for obtaining useful information from the complex systems of modern technology including many of our flotation and hydrometallurgical processes. Cybernetics offers the method by which complex systems which have been implemented as an art in the past can now be analyzed with all the discipline of a science. Mathematical techniques for achieving multiple correlation analysis have decided advantages over some of the other statistical methods.2-4 Multiple correlation does not require a series of experiments that have been rigidly planned as do many of the other statistical methods. For this reason, it can be used effectively for interpretation of information from op- erating plants, where planned experiments are impractical, as well as for laboratory experiments. First-degree multiple correlation has been used for many years, and was useful, but limited to linear or nearly linear relationships. The technique described in this paper provides a method for analyzing systems which may be non-linear. This particular technique is multiple correlation analysis in best-fitting third-degree parabolas. It is quite possible that lack of reference to the technique has been due to the overwhelming mass of computations it requires even for relatively simple problems. With the advent of computers, however, its use has become entirely feasible. For the benefit of those who may not be familiar with the subject, it might be well to pause at this point to discuss multiple correlation analysis — what it is and what it achieves. To go back to the old familiar fitting of a set of points with a best-fitting straight line by the least squares procedure, it is conceded that this a good method where there is only one independent variable influencing the dependent variable under consideration, and providing that the relationship is linear. In most fields of investigation, however, there are usually a number of factors exerting important influence, and they frequently bear relationships with the dependent variable other than straight line. Under these conditions, it is easy to see how misleading a simple correlation study might be. Multiple correlation can be used for any number of variables. Within the experience of the writer, this technique has been used to establish regression equations for determination of carbon rate, burden permeability, and production rate on iron blast furnaces, production rate on open hearth steel furnaces, life of molds for steel ingots, rolled steel tensile strength and various defects in rolled products, the performance of ore dressing equipment, and optimization of extractive metallurgical process variables. The discovery of mathematical correlation does not prove, per se, true cause-and-effect relationship, but simply establishes a hypothesis. If the regression equation can be used to make successful predictions of what will happen with future arrays of independent variables, then one can feel reasonably assured that true cause-and-effect relationships have been discovered.

Jan 1, 1968

By Charles A. Anderson

Arizona and western New Mexico contain 17 of the 25 leading copper mines in the United States. Production of molybdenite, lead, zinc, and by-product gold and silver is important. Precambrian ore deposits are largely limited to the Yavapai Series in central Arizona and most of the metal production has come from massive sulfide deposits, dominantly pyritic but containing different amounts of chalcopyrite, tennantite, sphalerite, and galena. Their origin has been interpreted by some geologists as hydrothermal replacement of schist, and by others as syngenetic deposits later metamorphosed. Most of the important ore deposits are of Mesozoic and early Tertiary age, dominated by the porphyry copper deposits spatially related to stocks, plugs, sills, or dikes of quartzbearing porphyritic to granular rocks. Host rocks for these deposits include the associated intrusive rocks, Precambrian schist and granitic rocks, Paleozoic limestones, Mesozoic(?) porphyritic andesite, and Mesozoic arkose and siltstone. Chalcopyrite and pyrite are the dominant hypogene sulfide minerals in the porphyry copper deposits, accompanied by minor molybdenite. The Questa deposit in New Mexico is largely molybdenite. Supergene sulfide minerals are chalcocite and minor covellite. Some ore bodies consist largely of hypogene sulfides, some are dominantly supergene sulfides, and others are mixed hypogene-supergene sulfides. Supergene oxide-copper minerals locally are important. Intense hydrothermal alteration accompanied the metallization in all of the porphyry copper deposits; five types are recognized, ( 1) propylitic, (2) argillic, (3) potassic, ( 4) quartz-sericite (without clay), and (5) lime silicate. The origin of the closely spaced fractures that contain ore minerals in intersecting veinlets is debatable; some geologists favor tectonic forces and others suggest cooling of magma or shrinkage due to alteration. Breccia pipes, veins, and limestone replacements account for some important deposits of Mesozoic and early Tertiary age, and presumably these are genetically related to the various intrusive rocks of this age. The St. Anthony deposit of Cenozoic age in southeastern Arizona is unique, consisting of a lead-zinc vein associated with later molybdenum and vanadium oxide-minerals. Cenozoic manganese deposits in western Arizona are an important resource in the Artillery Mountains, but the extent to which they may be exploited is a metallurgical and economic problem.

Jan 1, 1968

By S. Warren Hobbs

The section of the Northwestern United States that includes the northern Rocky Mountains and adjacent areas to the west and east is one of large mineral production and important mineral potential. The metallic ore deposits vary widely in age and type and their geologic settings are similarly diverse. A brief resume of the region's physiographic characteristics and geology sets the framework for the selected ore districts that are described in following papers and makes it possible to place these ore deposits in their proper reference to space and time.

Jan 1, 1968

By Johnson Crawford, Alan H. Hoagland

Zinc mining at Jefferson City began in 1854 with small scale production of oxidized ore from open pits. Significant production began in 1913 with the development of the Mascot Mine by the American Zinc Company. In 1965, four flotation mills were treating crude ore at the rate of about 12,000 tons per day and the Mascot-Jefferson City district currently is the largest zinc producing area in the United States. The producing mines, Mascot, Young, North Friends Station, New Market Zinc, Grasselli, Davis-Bible, Coy, and the Jefferson City, are 15 to 28 miles northeast of Knoxville in the Valley and Ridge physiographic province, an area of gentle relief lying between the more rugged Great Smoky Mountains and the Cumberland escarpment. The ore is strata bound, occurring essentially within a stratigraphic range of 200 feet in the Lower Kingsport and Upper Longview formations of Lower Ordovician age. In the lower strata of the mineralized section, the ore generally is found in coarsely crystalline elastic dolomite breccia containing silica and chert debris within a sequence of aphanitic limestones. The upper strata of the mineralized section are fine-grained primary dolomites that, in the ore zones, have been fragmented in mosaic patterns by solution collapse with the interfragmental space filled by white gangue dolomite and sphalerite. The mineralogy is unusually simple, sphalerite being the only important sulfide. Pyrite is very sparse. Dolomite gangue is abundant, silica was deposited in quite small amounts, calcite is minor, and fluorite and barite are very rare. The principal ore controlling structures are rubble breccia zones that were formed during the post-Lower Ordovician-pre-Middle Ordovician erosion interval by supergene solution as a phase of the development of a regional karst system of underground drainage that extended to' depths of at least 800 feet. The major Appalachian orogenic structures are post-ore and have been superimposed on the ore bodies. There is substantial evidence to support the current thinking of the writers that the ore deposits were formed at a depth not exc1~eding 800 feet.

Jan 1, 1968

By V. K. Grotzky, F. J. Fraikor

A number of investigators have noted the importance of various precipitation reactions on the properties of commercial-purity beryllium.1-5 Carrabine, for example, has demonstrated the interaction of iron and aluminum on the mechanical properties of hot-pressed polycrystalline beryllium.6 He considered the determining factor on elevated-temperature properties to be a reversible AlFeBe, precipitation reaction which could be directly related to the Fe/Al impurity ratio of the beryllium. Any aluminum in excess of the stoichio-metric amount required to form A1FeBe4 was presumed to remain primarily in the grain boundaries. We have observed, by transmission electron microscopy, such a grain boundary effect after various heat treatments of beryllium sheet. The starting material in this investigation was bare-rolled beryllium ingot sheet (0.001 to 0.005 in. thick), in contrast to the hot-pressed powder utilized by Carra-bine. It should be noted from the ingot sheet analysis shown in Table I that the Fe/Al weight ratio was near unity which would provide some free aluminum although the total aluminum and iron content was still small. Fig. l(a) shows some aluminum or aluminum-rich precipitates in the grain boundaries of a beryllium foil which had been quenched from 1200°C into brine at -TPC. Similar grain boundary precipitates were found, particularly at grain boundary intersections, in other samples quenched from 1100° and 1000°C. The length of annealing time at these elevated temperatures did not appear to substantially alter the amount of grain boundary precipitates, thus attesting to their relative insolubility. No matrix precipitates were observed other than the normal BeO and Be2C inclusions. A microprobe analysis of the larger precipitates at

Jan 1, 1968

By W. A. McCurdy, Joseph W. Leonard, T. S. Spicer

INTRODUCTION by T. S. SPICER and J. W. LEONARD Utilization from the Point of View of the Preparation Engineer The primary interest of the coal preparation engineer is process design, operation and maintenance to produce an acceptable product which can be sold at the greatest possible profit. Because of these interests, attention to the unrealized potential value of coal is sometimes neglected. The intent of this chapter is to alert the preparation engineer to the utilization possibilities of both the product as well as the tributary coal flow moving through a modem coal preparation plant. Thus, coal types having similar physical and chemical properties tend to become increasingly concentrated according to size, specific gravity and/or surface chemistry. The basis for any unrealized potential derives directly from the coal seam itself. Most coal seams consist of coal bands and benches which are sandwiched together in layers and which visually differ from each other by physical structure and luster. Randomly selected physical and chemical ranges determined from layers of coal in a single seam can easily differ by as much as 30 Hardgrove grindability indices, 0.30 of a specific gravity point, 20 percentage points of ash, six percentage points of dry volatile matter and 10 percentage points of total sulfur.1 Similar wide variations exist for calorific value, seam moisture content and undoubtedly, for any other conceivable coal test parameter which might be used for comparative purposes. These observations all point to the long established fact that coal is not homogeneous as conventional analytical methods might tend to indicate, but is instead a highly heterogeneous substance. Since both coal and associated minerals entering a preparation plant are highly heterogeneous, a multi-product potential beginning with certain flotation cell concentrates and ending with plant refuse may exist. Such a potential can and to a limited extent is achieved at some operations by drawing off coal according to size, specific gravity and/or surface chemistry differences from individual coal cleaning processes. Such a sequenced draw-off of coal of increasing ash increments could yield, among other products, chemical coals, coking coals, coals for pulverized fuel boilers, cyclone boiler coals, coals for cement plants, limestone, shale and clay. Basis for Coal Evaluation and Selection Despite the known heterogeneity of coal, the final analysis of a given coal product is customarily reported as a single average since coal has always

Jan 1, 1968

By A. Gittens

In two recent papers stevens13,14 has compared the methods used by various investigators to calculate the contribution of grain boundary sliding to the total creep strain. In previous work Gittins15 has shown that the strain due to grain boundary sliding Egb may be estimated from the lateral, d, and vertical, v, displacements of a longitudinal marker line as it crosses a grain boundary. He obtained the formula, where nL is the number of grains per unit length measured on the specimens before creep, and \p and ?2 are, respectively, the angle between the grain boundary and the stress axis in the plane of the surface and normal to the surface (see Ref. 13, Fig. 1). The subscript L indicates that observations are made in a longitudinal direction parallel to the stress axis. It was generally found more convenient to measure the grain size of a specimen before creep; this was necessary to characterize the specimen. Stevens13,14 however prefers to define Egb in terms of NL, the number of grains per unit length after creep. Since nL - NL(l + €1) where cr is the total strain, Eq. 1 11 becomes The quantities d and ?, can be determined directly from the marker lines, while v and ?2 are found by sectioning normal to the surface. In the interior when symmetry considerations suggest that v = d and ?1 - ?2 the strain due to grain boundary sliding may be estimated from a suitable internal longitudinal marker line by the equation To determine cgb at the surface using either Eqs. |1| or [2] requires a large number of observations, particularly if many estimates of cgb are required, and also it is impossible to determine the variation of cgh with creep strain on the same specimen because the specimen must be sectioned to determine ?2. Gittins15 found that for a number of materials the sliding vectors d and v were related to each other so that provided one was measured the other could be estimated. Also during creep, grain boundaries tend to migrate to meet the surface at angles close to 90 deg,16 so that the term nL(v/tan?2)L was comparatively small when 4,- 90 deg. By determining the frequency distributions of ?2 on control specimens this term can be estimated without sectioning the creep specimen. In this way an empirical equation based on Eqs. |1| and |2| enables cgb to be determined with reasonable accuracy with fewer observations of the angles and sliding components. For B brass, the relationship between the sliding vectors indicated that ceb = 0.85nLVL . In Table I of Stevens paper this equation is stated to be incorrectly derived. However it should be pointed out that this is an empirical equation derived from Eq. |1|, based on a knowledge of the relationship between d and v and on the frequency distributions of ?1 and ?2 for a particular material under given experimental conditions. It was used only when these relationships were known, to reduce the number of observations required to estimate cb. Therefore the comment "derivation incorrect does not apply. Gittins did in fact make use of Eqs. |1| and 131. Author's Reply I must apologize to Dr. Gittins for the inadvertent misrepresentation of his work. Other slight errors in Table I have been pointed out to me. Langdon (No. 12 Table I), Gifkins (No. 7, Table I), and possibly other workers did not measure the number of boundaries per unit length after creep (A') but the corresponding quantity bejove creep (n). As Dr. Gittins points out, a completely analogous set of equations to those given in the paper can be derived by the same method: using the number of boundaries per unit length before instead of after creep. The basic equations corresponding to Eqs. [2] and 171 of the paper, from which all the others can be derived, are

Jan 1, 1968

By R. DiBella, H. Biloni, G. F. Bolling

A study of the detailed relationship between solidification substructure and microsegregation in dilute tin alloys has been continued. New observations reveal that depressions form at the solid-liquid interface not only as an initial form of segregation but throughout the range of increasing constitutional supercooling. In order to show the importance of this node formation it proves convenient to make two simplifications. Although substructure changes continuously as constitutional- supercooling increases,&apos; the following discrete stages may be used for discussion: 1) the planar solid-liquid interface; 2) ordered nodes, or depressions at the interface;&apos; 3) two-dimensional or elongated cells;3 4) regular or hexagonal cells;4 5) distorted cells, or hexagonal cells with branches;4 6) dendrites. It is also convenient to ignore observations made near grain boundaries which interact with the cellular substructure.2-4 And, it should be clearly pointed out that all singular depressions at the solid-liquid interface will be called nodes. Heretofore, the term "node" has been used without clear justification to describe both the truly isolated depression and the junction of cell walls appearing in a later stage of segregation. This usage is continued because it seems proved by the observations. Standard systematic growth of tin crystals was undertaken over a broad range of constitutional supercooling using various added solutes. Except for one or two chance observations, this research failed to reveal any appreciable range of growth conditions over which a disordered array of isolated nodes exists. Even though &apos;some finite range of random instability must exist, it is now concluded that stage one passes very rapidly to stage two. Next, after confirming that stage two passes to stage three by the elongation of isolated nodes: a reexamina-tion of stages three, four, and five followed. Standard metallography showed that pockets of higher solute concentration (for ko < 1) became more numerous in cell walls the more severe the growth conditions. These high-concentration regions must arise from depressions; however, in stage three their segregation is not distinguishable from the segregation of the nodes which join cell walls together. It seems, therefore, that the presence of nodes is causal in the formation of new cell walls, and that the mechanism by which stage three passes to stage four is initiated by nodes. If a similar reasoning is followed, the separation of stage four from stage five appears to be just a convenience that has arisen from the decanted interface observations made in the past. The present observations again show that more severe growth conditions relate directly to an increase in the number of nodes in the hexagonal cell walls. These nodes apparently serve as the origin for lines of segregation extending within the body of a cell, and can thus be assumed to represent the earliest form of branching,* as shown here in Fig. 1. The examination of stage six involved decanted-interface structures as in Fig. 2, which are similar to those considered by Rutter and Chalmers,5 Plaskett and winegard,6 and Hellawell and Herbert,7 and where distinct protrusions are each surrounded by a depressed boundary. The corresponding microsegregation behind the interface, but not far enough behind to allow a smearing of the segregation because of diffusion,4 is shown in Fig. 3. Both the shape of the decanted interface and the segregation pattern behind it

Jan 1, 1968

By Robert G. Beverly

The presence of radioactivity in uranium mill wastes has resulted in somewhat unique waste disposal methods. In addition to the common problems of disposing of large quantities of solid wastes, neutralizing acids, minimizing dissolved heavy metals, and clarifying all liquid effluents, the uranium mill operator must sample and analyze liquid effluents for micro-micro quantities of radionuclides such as, radium-226, thorium-230 and lead-210. Special disposal methods or decontamination procedures are required to meet the stringent limitations established by the U. S. Atomic Energy Commission on the concentration of radionuclides in liquid effluents. Routine monitoring of the receiving stream is also normally required. In recent years there has been a growing concern about the radioactivity remaining in the uranium mill tailings, particularly at the sites of shut-down or dismantled mills. The State of Colorado, in cooperation with the industry, has adopted regulations for stabilization of inactive uranium mill tailings. The Mining and Metals Division of Union Carbide operates mills for the recovery of uranium and vanadium at Uravan and Rifle in Colorado and a mill in the Gas Hills of Wyoming for uranium production. The company also owns former mill sites on which mill tailings are located at Maybell, Rifle, and Slick Rock in Colorado and at Green River, Utah. The purpose of this paper is to describe the methods used by a few uranium mills, largely those operated by Union Carbide Corporation, to dispose of radioactive wastes, to discuss briefly the regulations under which the mills operate, and to present reference information on the subject.

Jan 1, 1968

By R. H. Oitto

To determine whether reflectors could substitute for the trip lights referred to in the Federal Mine Safety Code, the Bureau of Mines studied trip safety devices under simulated haulageway conditions. The noticeability of reflectors compared with trip lights and fluorescent panels was evaluated from distances of up to 850 feet with light source intensities of up to 1-6 foot-candles (ft c). Reflectors tested consisted of a reflective lens in a holder secured to a frame that can be attached to a trip. Reflectors were found to be suitable for use as a trip safety device. In fact, for the conditions in many underground haulageways some reflectors would be more effective than a permissible trip light.

Jan 1, 1968

By A. D. Zunkel, A. H. Larson

Equilibrium antimony contents of pb-sb alloys in contact with PbO-Sb2O3 slags containing less than 45 mole pct Sb203 uleve determined at 650&apos;, 700°, and 750°C in an inert atmosphere. In this ten~pevature range, the antimony contmzt of the alloy increased with increasing temperature at all slag compositions. The PbO-Sb203 phase diagram below 28 mole pct Sb2O3 was determined by thermal analysis and by application of a log sbZ4/y$b0 us plot determined from the equilibrium-activity data. The resulting phase diagram showed a eutectic at a temperature of 604°C and a comfiosition of 21.6 mole pct Sb2O, with a maximum terminal solid solubility of Sb203 in PbO of 5.6 mole pct. These results are compared with existing data in the literature. In the past three decades, only a small amount of experimental work has been done on the slag-metal equilibria in the Pb-PbO-SbaO3 or the analogous arsenic and tin systems. These systems are important in commercial lead-refining processes such as softening and dross fuming since it is impurities such as antimony, arsenic, and tin in lead bullion and Sb2O3, As2O3, and SnOz in lead drosses which must be re-

Jan 1, 1968

By Dwight K. Smith

Fly ash as an additive for oil well cement was introduced to the oil industry by the Halliburton Company in 1949. Since its early usage in the Illinois area of the U. S., the total amount of fly ash pumped into wells has exceeded 30 million sacks, The advantages of using fly ash-portland cement mixtures in wells are fundamentally the same as for concrete except the conditions of placement and curing are variable and the nomenclature of properties are expressed somewhat differently. In some instances deep wells have been cemented with mixtures of fly ash and hydrated lime together with an activator which functions as a catalyst for setting. This fly ash-lime formula has many advantages for high temperature-pressure conditions found in wells.

Jan 1, 1968

By P. Chaudhari, Michael B. Bever

The heat of solution at infinite dilution of selenium in bismuth, the heat of mixing of selenium and bismuth, and the limit of solubility of selenium in bis~rzuth have been determined at 573, 623; and 663°K by metal solution calorimetry. The heat of forrrzation of the compound Bi2Se at these temperatures has been determined from the heat effects associated with the precipitation of the compound from a saturated solution oj selenium and bismuth. The published information on the thermodynamic properties of the system Bi-Se is limited. The heat of solution at infinite dilution of selenium in bismuth at 623°K has been measured.&apos; The heat of formation at 273 K1 and room temperature2 and the heat capacity at 80 K3 of the compound Bi2Se3 have been reported. An estimate of the heat of formation of the compound BiSe at room temperature has been published.2 Information on the phase relations in the system Bi-Se is available.&apos; In the investigation reported here the following quantities have been determined at 573", 623", and 663°K: 1) the heat of solution at infinite dilution of selenium in bismuth, 2) the heat of mixing of selenium and bismuth in bismuth-rich solutions, 3) the limit of solubility of selenium in bismuth, and 4) the heat of formation of the compound BizSe. These quantities were determined by the addition of selenium to bismuth-rich solutions in a metal solution calorimeter. The determination of the heat of formation at the tem- perature of the calorimeter bath involved the precipitation of the compound from a saturated solution in the calorimeter. 5,6 This method differs from that commonly used which requires the addition of the compound and of a mechanical mixture of its components and yields the heat of formation at the temperature from which the additions are made (273 K EXPERIMENTAL PROCEDURE AND CALCULATIONS The solution calorimeter has been described in detail.&apos; Pure bismuth (99.999+ pct) was used as the bath at the start of a run. The calorimeter was calibrated with small amounts of bismuth added from 273°K; the differences of the heat contents of bismuth at 273°K and the temperatures of the baths are listed in Table I. After the calibration, additions of hexagonal selenium (99.999+ pct) were made. Loss of selenium by evaporation was negligible. No unusual experimental difficulties were encountered.9 The differences in the heat contents10 of selenium at 273°K and the temperature of the bath, listed in Table I, were subtracted from the measured heat effects to give the "adjusted heat effects". The methods by which the heat of solution at infinite dilution, the

Jan 1, 1968

By R. W. Shoenberger, J. D. Clendenin, W. L. McMorris, N. Schapiro, B. R. Kuchta, A. A. Terchick, R. J. Gray, J. G. Price

INTRODUCTION * The United States is fortunate in having enormous reserves of metallurgical-grade coals. Although these coals are better in quality and more accessible than most coals found throughout the rest of the world, the best grades of these coals are being depleted. Consequently, more efficient exploration tools and techniques, such as advanced methods of core drilling and logging, correlation by palynology,** stratigraphy, paleontology and petrography are being used to help assess the extent and quality of the remaining coal reserves. Exploration and assessment of new and existing coal properties become of utmost importance in determining (1) the economic justification for mining the coal, (2) the optimum design of the preparation plant and (3) the most effective use of the coal. Fortunately, the cost of mining coal has remained stable because of better mine planning, more efficient operations and increased mechanization of mining operations. However, increased mechanization raises the amount of impurities in the coal mined, and this requires more and better coal beneficiation to meet the more stringent quality requirements set by the market. Besides, mechanical miners also produce relatively fine coal and, to ensure maximum liberation of impurities, much of the coal presently being used must be crushed to a finer size prior to preparation. The bulk of all coals presently used in this country is mechanically cleaned, much of it at a lower specific gravity than in the past. This necessitates the use of new and improved processes and equipment for coal washing and recovery, such as heavy-medium cyclones and vessels, and froth flotation cells. However, because wet-cleaning processes are pre- dominant in the United States and fine coal retains large amounts of moisture, the increased production of cleaned fine coal accentuates the need for new or improved methods and equipment for dewatering and drying this coal. The larger amounts of coal being beneficiated and the use of new and improved beneficiation processes will aid in controlling and ultimately eliminating sources of pollution. Modem coal markets demand coals that meet rigid specifications. Most coals are purchased under contracts that specify moisture, ash, and sulfur contents, or heating value, depending upon the end use. There has also been a growing trend toward specifying other properties, including particle size and coking capability. These specifications may include not only the * Editor&apos;s note: Because of the numerous and varied contributions of the associate authors of this chapter, the text does not differentiate between sections prepared by each individual as has been done in other chapters. ** Palynology is the study of plant microfossils, especially spores, pollen, and other types of fossils not usually studied by paleontologists.

Jan 1, 1968

By L. A. Haas

A kinetic study of the carbon deposition reaction was undertaken by the Bureau of Mines as part of a broad investigation of metallurgical reactions in the iron ore blast furnace. The disproportionation of carbon monoxide on iron pellets was investigated at carbon monoxide pressures between 0.5 and 2 atmospheres (absolute) and temperatures from 400° to 1,075° C. Gas flow in the range from 0.25 to 0.85 standard liter per minute was found to have little effect on the reaction velocity. The addition of nitrogen and helium to caron monoxide exerted only a dilution effect on the rate of carbon deposition. However, an addition of 1 percent hydrogen increased the rate about 100 times. Small amounts of carbon dioxide in the inlet gas exerted little effect on the rate of carbon deposition. The maximum rate for carbon deposition in the first 2 hours occurred at 550° C. The apparent molar activation energies at various stages of the reaction were found to vary from 13 kcal initially to 36 kcal during the latter stages of the reaction. The reaction rate behavior was tentatively explained by an adsorption step followed by the diffusion of iron through a shell of inactive iron carbide.

Jan 1, 1968

By Edgar L. Weinberg, W. Horatio Brown

The Austinville-Ivanhoe lead-zinc deposit occurs in the Lower Cambrian Shady dolomite. This deposit is located in southwestern Virginia in the faulted and folded Appalachian Valley and Ridge province. The ore bodies resemble the chimmey and manto deposits of northern Mexico and are formed by replacement and filling. They are confined to certain favorable zones of the Austinville and Ribbon members of the Shady. Structural and stratigraphic factors combine to control the location and form of the ore bodies. In certain places secondary oxide enrichment of the zinc minerals has contributed to the economic development of the area. It is concluded that the ore is epigenetic and is deposited by hydrothermal solutions rising through the fault "plumbing." Classification is epithermal-telethermal.

Jan 1, 1968

By D. F. Stein

In spite of the apparent usefulness of autoradiography in demonstrating segregation, it has had very limited success in demonstrating grain boundary segregation. Because of this limited success, a model system amenable to mathematical analysis was devised to determine which variables in the experiment are most important. As a result of these calculations, it was concluded that autoradiograPhy is a rather insensitive technique to measure grain boundary segregation. The range (energies) of the emitted particles (ß and a) must be low, and the concentration of the radioactive speczes at the grain boundary must be (in general) two or three orders of magnitude greater than the concentration within the grain. Because of these very restricted conditions , the limited success of the technzque is not surprising. In spite of the apparent usefulness of autoradiography in demonstrating segregation, it has had very limited success in demonstrating grain boundary segregation. Sulfur segregation in iron1 and possibly polonium segregation in Pb-5 pct B1 2 alloys are the only autoradi-ography experiments that have demonstrated segregation to grain boundaries in metals without the formation of a second phase. Segregation to a boundary without the formation of a second phase is often called Gibbs&apos; absorption and is discussed by McLean in Chapter 5 of Ref. 10. There are several394 experiments showing grain boundary diffusion of a radioisotope, but this type experiment is not representative of equilibrium between the concentration of an element at a grain boundary and that in bulk, so it will not be discussed in this paper. In an attempt to determine if temper embrittle ment of low-alloy steels was associated with segregation of antimony to grain boundaries, a program to use auto-radiography (using Sb-125) was initiated. Even though other measurements strongly suggest that segregation is occurring during embrittlement, no evidence of grain boundary segregation was observed in the auto-radiography experiments. An attempt was also made to detect segregation of carbon (using C-14) to grain boundaries in iron during slow cooling. There is again strong indirect evidence7 that segregation occurs during such a treatment, but the autoradiography experiment gave no evidence of such segregation. Because of the failure of these experiments and the general lack of success by our metallographic unit in measuring grain boundary segregation using autoradi-ography, a model system amenable to mathematical analysis was devised to determine which variables in the experiment are most important. MODEL SYSTEM The model system is illustrated in Figs. 1 and 2. It is a semi-infinite bicrystal with a single grain boundary perpendicular to the top face. The width of the grain boundary, W, is defined as the region to which segregation has occurred and it is assumed that this region is of constant composition. The assumption of an infinite dimension is for mathematical reasons but the results of such an analysis (as will be demonstrated later) are valid for even very small specimens. It also is assumed that the measurement is not limited by means of detecting the radiation (photographic emulsions, counters, and so forth) but that the means of detecting radiation is linearly sensitive to the radiation and has infinite resolving power. The distance y is the perpendicular distance from the center of the grain boundary to the point at which the background radiation is measured and x is the integration variable. CALCULATION FOR BETA PARTICLES Two values of the intensity of radiation will be calculated, the intensity at the center of the grain boundary and the intensity far from the grain boundary. The radiation at the center of the grain boundary can be calculated in the following way. Assume a grain boundary of width W having a uniform concentration equal to Cgb + Cb where CGb is the excess concentration of the element under consideration at the grain boundary and Cb is the bulk concentration. The intensity of radiation, IgB, at the center of the grain boundary, is a consequence of the amount of radioactive material, decay rate, absorption, and geometrical factors which can be represented mathematically by the following expression:

Jan 1, 1968

By James J. Bailey

Percussive drills have been in commercial use for many decades. Until relatively recently there was little serious effort to analyze the stresses in such devices in any detail. Within the last few years such analyses have been developed and have been reported by a number of authors.1-4 We present here an investigation of the impact systems of a family of conventional down-hole drills with optimization the objective. We have assumed that maximum drilling speed was the quality most desired and that this was to be achieved within conventional practice. In fact the methods that are demonstrated in principle below can readily be adapted to other percussive devices, whether conventional or not, and to other constraints. SOME PERFORMANCE PARAMETERS FOR PERCUSSIVE DRILLS Consider a percussive drill with an air motor operating with the following parameters: p-supply air pressure a-effective piston area W-piston mass S-piston stroke If we consider a simple (constant pressure) cycle, the following relationships can be derived. The blow frequency [N~ pa lie WS 377]

Jan 1, 1968