Search Documents

By A. G. Guy

In a special type of electrodiffusion experiment the entire specimen is at constant temperature. The vacancies are then created at one end of the specimen and flow to the other end where they are destroyed. The energy required to operate the corresponding sources and sinks results in a super saturation of vacancies at one end of the specimen and an under -saturation at the other end. This gradient in vacancy concentration produces a chemical-diffusion flux, J(D), of vacancies in addition to the flux, J(E), caused by the electric current. Using the experimental data of Ch. Herzig,5 it is shown that a super saturation of 1 pct can cause J(D) to be about 25 pct of J(E), and thus account for the anomalous behavior of short specimens. THERE are advantages in a phenomenological treatment as contrasted to an atomistic one. For example, there are many reactions involving the element copper that are quantitatively and usefully understood from a phenomenological viewpoint, even though electron theory is not yet able to predict whether copper should be fcc or cph.' Similarly, the lack of a complete atomic theory of vacancies need not prevent the development of a treatment based on thermodynamics and chemical kinetics. In the following discussion, models will be used for the vacancies and for the mechanisms by which they move or are created or destroyed, but the phenomenological treatments are not dependent on the details of these models. The important product of a phenomenological analysis is an equation that describes the relation among the measurable quantities determining the behavior of the system. Based on such an equation, experiments can be performed to study these quantities in detail. Eventually atomic theory will supply an adequate theoretical base for the phenomena in question. A chemical species whose chemical potential was invariant during reactions in binary and ternary systems of varying composition would indeed be an anomaly. Yet this is the role that has frequently been assigned to the vacancies in pure metals, in dilute solutions, and even in ordinary alloys. The weight of available evidence supports the view that supersatu-rations of vacancies are on the order of 1 pct in usual diffusion processes.' Although it may seem strange that such a small deviation from equilibrium could significantly affect the thermodynamic properties of the vacancies, it is well known that the driving force for an ordinary chemical reaction is the departure of the components from their equilibrium state. Similarly, the reaction of vacancies that results in the formation of pores in various types of diffusion3 can reasonably be attributed to the supersaturation of vacancies. In the present paper, it will be shown that small degrees of supersaturation can significantly affect the kinetics of the diffusion process itself. ISOTHERMAL ELECTRODIFFUSION Two different experimental techniques are convenient for studying the behavior of vacancies in a pure metal in the presence of an electric field. Gilder and Lazarus4 studied self-electrodiffusion in a gold specimen in which only the central portion was at high temperatures. In this case the significant vacancy sources operate inside the specimen in the presence of a temperature gradient. In the laboratory of Th. Heumann a method has been devised for studying self-electrodiffusion at constant temperature.5 In principle, there is then no effect of thermodiffusion. It will now be shown why in this case the significant ATungsten disks \^^ ^^ ^Gold disks^^ ^^"T>.... "TTZA ? Up Iy'7 markers ///// ////// initial plane p I y/y/y of joining \I 7//// V7//A_________I_________V//// -I 0 +I Distance from center of specimen (a) -— Direction of flow of electrons —Direction of flw of vacancies %yy} Matano I z~irkendall /%W, vy/A inlerfacej "interface ///// -} HfiK- +/ 0 Distance from center of specimen (6) Fig. 1—-Schematic illustration of the essential features of isothermal self-electrodiffusion. (a) Initial condition of specimen. (b) Condition of specimen after electrodiffusion.

Jan 1, 1970

By R. S. Rickard, H. D. Peterson, J. D. Miller, M. C. Fuerstenan

Pure chrysocolla is floated with chelating agents that form insoluble complexes with copper at ambient temperature. Complete flotation is obtained with potassium octyl hydroxamate as collector at pH 6. Flotation response is enhanced with increased temperature when low additions of hydroxamate are involved. A natural ore was floated with 0.4 1b per ton octyl hydroxamate at pH 6.5 and 58°C, and a flotation recovery of 76% was obtained with a concentrate grade of 31.6% copper. The flotation characteristics of the oxide copper minerals, malachite, azurite, and cuprite, have not presented the difficulty for concentration as have those of the copper silicate, chrysocolla. The copper carbonates and oxides respond reasonably well to flotation with conventional collectors, whereas chrysocolla will not respond to flotation with fatty acids or xanthates under normal flotation conditions. In this view then, other reagents will have to be devised to function as collectors for chrysocolla. The most obvious general class of reagents for this purpose would seem to be the organic copper chelating compounds. The utility of chelating agents as collectors in flotation systems has already been demonstrated. For example Vivian1 has floated cassiterite using ammonium nitrosophenylhydroxylamine. Holman2 studied the flotation of nickel oxide ores with dimethylglyoxime and also suggested the use of taurine on oxidized lead ores. A rather detailed study on the application of certain chelating agents to some flotation systems was presented by Gutzeit.3 This work indicated that the formation of surface insoluble chelates is probably responsible for flotation in many cases. The role that soluble chelating agents assume was also presented, that is with effective removal of polyvalent cations by complex formation, effective depression of quartz can be obtained. DeWitt and Batchelder4,5 have shown that oximes function well as collectors for chalcocite, malachite, azurite, and cuprite. Ludt and DeWitt6 have presented the possibility of using dyes, such as octyl malachite green, as a collector for chrysocolla. These works presented by DeWitt et al suggest that organic copper chelating compounds offer considerable promise for concentrating chrysocolla, but that the most suitable chelating reagent from the standpoint of cost and flotation response has yet to be determined. The present investigation was undertaken to study the flotation response of chrysocolla to selected copper chelating compounds, that is ethylenediamine, hexamethylenetetramine, potassium octyl hydroxamate, dimethylglyoxime, and benzoin a-oxime. EXPERIMENTAL MATERIALS Chrysocolla: The chrysocolla used in the microflo-tation studies was from New Mexico and analyzed 20.8% copper. X-ray diffraction showed this material to be amorphous in character, but some faint lines of quartz were noted. A natural oxide copper ore from Utah was also used in the investigation. This ore contains malachite principally but also contains chrysocolla and tenorite together with some sulfide copper. The sulfide copper comprises from 15 to 20% of the total copper content of the ore. Water: Conductivity water was used in the microflo-tation experiments, while Golden tap water was used in the experiments with the natural ore. Reagents: Reagent grade n-amyl alcohol was used as frother in the experiments with pure mineral, while MIBC was used in the work with the ore. Ethylenediamine, hexamethylenetetramine, dimethylglyoxime and benzoin a-oxime were reagent grade in quality. Pure potassium octyl hydroxamate was prepared as follows: 1) 1.0 mole of KOH in 140 cc of methanol was combined with 0.6 mole of hydroxyl-amine hydrochloride in 240 cc of methanol at 40°C (KC1 precipitates under these conditions and to effect complete removal of KCl, the system was cooled to 10°C and filtered), 2) a light methanol wash was then given the KC1 cake, 3) the filtrate was agitated at room temperature and 0.33 mole of the methyl ester of the organic acid (i.e. methyl octanoate) was

Jan 1, 1965

GENERAL GEOLOGICAL DESCRIPTION The uranium mineral appraisal herein described was made for an ore deposit in New Mexico. The uranium mineralization occurs as roughly tabular to lens-shaped deposits of varying thickness within the sandstone of the Jackpile formation of Jurassic age. The mineralization occurs at several horizons within the Jackpile formation, but is not always confined to specific beds. It often transgresses across stratigraphic layers, as demonstrated when attempting correlation of uranium gamma anomalies between adjacent drill holes. Preferred mineral trends have been established in some parts of the deposit, but are not always predictable when attempting to extrapolate beyond the zones defined by drill hole sampling. MANAGEMENT OF DRILL HOLE SAMPLE DATA All of the drill hole sample data used in the appraisal were obtained from interpretation of gamma-ray logs. A brief description of gamma-ray log sampling is given in Chapter 2. Two preliminary steps are involved in preparing gamma-ray logs into sample data normally acceptable for computer manipulation. 1) The gamma analog trace produced by the downhole probe must be digitized, i.e., counts-per-second (CPS) are recorded for each 0.15 m (1/2-ft) interval across the gamma-ray anomaly. The work is usually done on a "digitizer" while following the analog trace with an electronic stylus on a special tablet or table. The other alternative is to do the work manually. Some of the newest downhole logging equipment produces a magnetic tape output which can be read by a computer. 2) The gamma-ray CPS values must then be converted to equivalent U308 assay values, taking into consideration all appropriate correction factors. The US Atomic Energy Commission, now part of the Department of Energy, developed the theory and algorithm for this conversion in the 1960's, and though the work can be done manually, it is best done with the GAMRED (gamma-reduction) computer program. Fig. 14-1 illustrates a typical analog trace produced by the probe instrumentation, including gamma-ray trace (left), self-potential electric log (center), and resistivity log (right). Fig. 14-2 shows a form of the computer output after the analog data has been digitized to 0.15-m (1h-ft) intervals and converted to percentage U308 values for the same hole. The U308 grade bar graph on the right permits rapid visual inspection of anomalous values by depth and elevation. The converted U308 sample data were next processed by the SURVEY program that assigned to each assay interval [0. 15-m (1h-ft)] an X Y Z coordinate, taking into account all deviations indicated from downhole survey information. The output file of the SURVEY program was listed on the line printer for examination by project geologists, and also became the main input file for the URAN/ COMP compositing program, which is designed to group individual 0.15-m (/-ft) U308 sample values into larger intervals representing discrete anomalous zones according to a series of specified parameters entered into the program by the user. Composite U308 intervals were computed by the URAN/COMP computer program, the logic of which may be briefly described as follows: Step 1 The program searches for the highest U308 value in the hole and builds a composite by adding the highest grade interval on either side so long as the added value is greater than a minimum acceptable grade, and the total composite, after addition, meets minimum GT (grade times thickness) constraints. Step 2 The program loops back to find the next highest assay value in the hole not already included into a composite, until all anomalies above minimum cutoff grade are composited. Step 3 Individual composites are combined if they are closer than a specified minimum waste thickness, and the resultant composite grade still meets GT minimums.

Jan 1, 1980

By Leons Kovisars

Introduction Competitive analysis is the collection and evaluation of data on a product, a product line or on an entire industry. Much of the focus of competitive analysis centers on production volume and the price targets of the competitors. In actual practice capacity may be used in place of production volume. Similarly, unit production costs and individual producing units - mines, mills, smelters, refineries - may be the targets of the analysis. The purpose of competitive analysis is to provide information for strategic planning. The analysis will locate the position of the company in the industry and define the competitive margin -- or lack of a margin - between the company and other producers. The analysis can show the current situation and may be expanded to examine the outlook for the future. The forecast option is particularly valuable because it will show the opportunities for new project development or the expansion of current production. Similarly, the forecast will show the potential threat from new entrants, and may provide early warning to reconsider operations that may become uncompetitive in the future. Production cost analysis is a clearly understood means to evaluate producers and estimate the outlook for their profitability. The cumulative cost for the industry outlines the supply structure and defines the marginal cost of production used in developing price forecast as explained in the sub- sequent section of this paper. Competitive analysis is particularly important to the mining industry, notably to metal producers. The final product is typically a purified metal conforming to standards, and interchangable with the output of other producers, i.e. a fungible commodity. Brand loyalty is questionable in the mineral industry. Consumers will show a preference for specific brands, but this preference will be limited to a premium of several percent over the general market price. Price and assurance of supply are the keys to marketing success. Assurance of supply depends on geopolitical considerations and production capabilities. Price will be closely related to cost of production and a thorough competitive analysis should describe the cost structure of the industry. This snapshot will locate one's own position and provide an immediate and readily understandable evaluation of the hazards and opportunities inherent in this position. In the following section we shall discuss elements, methods and sources for competitive evaluation. ELEMENTS OF COMPETITIVE ANALYSIS The practice of systematic collection and analysis of data on competition is hardly a new concept; see, for example, Wall (1) or Porter (2). However, most discussions have been in the context of conventional industrial or manufacturing industries, with a focus on product lines and brand marketing. These considerations are not irrelevant to mining but they do have only a limited application. The key to success in the mining industry is minimizing the cost of production. However, this simple concept becomes complex when we consider relevant costs and the planning horizon. Production costs include the factors consumed in production, namely labor, fuel, energy, materials and supplies. The cost also includes purchased and contracted services such as freight, smelting and refining, sampling and sales required to convert ore to the finished metal. Royalties and ad valorem taxes paid on gross production are direct expenses, as is the cost of administration required by the production units. The sum of these outflows is the total cash cost, the expense that has to be paid in cash in order to continue production. Indirect costs incurred by a producer will commonly include allocated headquarters expenses, as well as the capital charges associated with equity investment and debt. Profit is not generally considered an indirect cost even though it represents the cost of using the owner's capital; similarly, income taxes represent the government's participation in the profits of the enterprise. Interest payments are considered as a direct expense in some cost studies, but many competitive evaluations would consider

Jan 1, 1985

By E. E. Thurlow

The Geology Div. of Northern Pacific Railway Co. has adapted to its exploration efforts field procedures for geochemical sampling and semi-quantitative analysis which have been developed through research by the U. S. Geological Survey. The sampling is done in conjunction with reconnaissance geologic mapping on aerial photographs or during field checking of maps which have been prepared largely by photo-geologic interpretation. Stream sediment or soil samples are taken and readily soluble combined heavy metals are extracted with ammonium citrate followed by colorimetric titration with dithizone at the sample site. The effectiveness of this approach has been demonstrated both in positive and negative results, thereby assisting in the elimination of large areas of land from further immediate attention and in providing targets for followup exploration. An occa sional sample is submitted for spectrographic analysis as a check on the possible presence of other elements of economic significance. Field laboratory procedures are also being implemented for determining molybdenum, mercury, and other metals which may be valuable in themselves or useful as pathfinder elements in outlining mineralized areas. A lead-zinc occurrence in Oregon and a copper deposit in Montana were readily detected and outlined by stream sediment and soil sampling and a heavy metal anomaly that lacks obvious interpretation has been found in northwestern Montana. Detailed mapping and additional sampling are followed by other exploration techniques if warranted. Northern Pacific's program of reconnaissance mineral evaluation of company-owned lands and adjoining areas was outlined in a paper presented at the American Mining Congress meeting in Las Vegas four years ago. That report included policies and procedures with respect to mineral development on Railway Co. lands and may be referred to for information on these matters.1 In a sense this paper is a progress report on the use of geochemical prospecting in Northern Pacific's continuing mineral evaluation program. At this time there are positive results but as yet there is no real success story in the form of a minable ore body. GEOCHEMICAL PROSPECTING PROCEDURES The decision to use geochemistry as a reconnaissance exploration tool must be followed by research into sampling and analytical methods and into the interpretation of results. Various analytical methods were tried and evaluated by the Geology Div., including hot and cold acid extraction with and without fusion of the sample, panning and magnetic separation followed by dithizone testing of the magnetite, and cold aqueous extraction of metallic ions followed by indicator tests. Samples were first sent to the laboratory for analysis; later field laboratories were established and now virtually all testing is done at the sample site. It was concluded that, where applicable, the quickest dependable methods for reconnaissance use are the dithizone field tests for readily extractable heavy metals. This involves the simultaneous treatment of a sample, usually of soil or stream sediment, with two immiscible liquids; one a cold aqueous extractant (ammonium citrate) and the other a solution of dithizone in toluene or xylene.2 Dithizone is a colorimetric indicator that reacts quantitatively with copper, lead, zinc, and several other metals to form colored complexes in organic solvents. Results may be expressed in ml of 0.001 pct dithizone that are required to reach the blue end point, or calibration of the test results can be carried out with standard solutions of zinc; conversion factors would then be expressed in ppm, zinc equivalent. Calibration of dithizone solution with zinc standards indicates that 1 ml of 0.001 pct dithizone is equivalent to approximately 0.25 ppm of zinc. An authoritative report on dithizone field tests authored by H. E. Hawkes in the June-July 1963 issue of Economic Geology* states "The appeal of these techniques has been the simplicity and speed of the determinations as compared with more tedious laboratory determinations of trace metals in weathered rocks, soils, or plant materials. This obvious appeal, however, has often been more than matched by misuse of the method in such a manner that the results are

Jan 1, 1964

By Edwin F. Brush, John Chipman

Published data on the activity of carbon in binary and ternary austenite at 1000°C are reviewed. The composition variables are . The coefficient, Vj, has the value for substitutional elements but may be assigned a ualue -1 for silicon to effect a simplification on the mathematical treatment. The activity coefficient PC = is obtained from gas equilibrium data. For the ternary systems studied the Henrian activity coefficient is given by the expression: The principle advantage in cornparison with the analogous expression in terms of atom fractions is found in the fact that for most systems the final term and in many the last two terms are zero. Values of the interaction parameters are tabulated and the graphical comparison of the equation with experirt~ental data is sho,wn in several figures. The thermodynamic properties of the solid solution, austenite, are of considerable importance in the heat-treatment of alloy steels and in other aspects of ferrous metallurgy. Early studies embodied in the Fe-C diagram have been extended to include other binary and some ternary diagrams. Our best hope of obtaining a useful thermodynamic treatment of reactions in complex alloy steels will not be found in quaternary and quinternary phase diagrams but in determinations of activities and interaction relations among the several solute elements. The foundation for such a development was laid by smith' in his early studies of the activity of carbon in Fe-C alloys and his subsequent work on Fe-C-Si, Fe-C-Mn, Fe-C-Ni, and Fe-C-Co solid solutions.2"4 Other observers have also made noteworthy contributions and these will be discussed and correlated here in the light of a somewhat simplified mathematical treatment of solute interactions. Fe-C AT 1000°C In a recent review of the thermodynamic properties of binary Fe-C austenite it was shown that the simple mathematical treatment employed by smith' was capable of describing all the published results on this solution. The treatment utilizes the atom ratio, yc = nC/nF,, rather than the atom fraction. The activity of carbon is proportional to the equilibrium gas ratio, either measured on a scalk in which the activity of graphite is taken as unity or, alternatively, aC may be set equal to yc at infinite dilution. In either case the ratio aC/y = (PC, the activity coefficient. It was found that the experimental data of smith1 and those of Diin-wald and wagner; Bungardt, Preisendanz, and Lehn-ert,' and Scheil, Schmidt, and Wiinnings at temperatures of 800" to 1200° C as well as reliable data on the solubilities of graphite and cementite could be represented by the equation for which graphite is the standard state: The data on alloyed austenite have been obtained at 1000°C. For this temperature, the "Henrian" activity coefficient (which is unity at infinite dilution) is: FOr an interstitial solute such as carbon in austenite it has been shown by statistical mechanicsg that the activity in the infinitely dilute solution is proportional to the ratio of the number of lattice sites occupied by carbon to the number of yet unfilled lattice sites. A variable zz proportional to this ratio serves as a useful measure of concentration:" in which b is the number of lattice sites provided by each atom of solvent; in austenite b = 1. The Henrian activity approaches zz at infinite dilution and the ratio a is the activity coefficient. The effect of a change in concentration is then given by: It has been shown further that in some systems the derivative in Eq. [4] remains constant over a wide range of concentrations. In such a case second-order terms become negligible and the Henrian activity coefficients is:

Jan 1, 1969

By S. R. B. Cooke, Y. S. Kim, I. Iwasaki

lron oxides or the gangue minerals of iron ores can be made to float, depending upon the choice of collector. The selectivity of the separation is controlled by the accompanying chemical and operating conditions. In this report the findings on the general flotation characteristics of magnetite are summarized and the results are compared with those obtained for other iron oxides. Depending upon the choice of collector, either the iron oxides or the gangue minerals of iron ores can be made to float, the selectivity of the separation being controlled by the accompanying chemical and operating conditions. The mechanism by which a collector exerts preferential affinity for either group of minerals has been a subject of extended discussion. Previous investigations on the electrokinetic properties and flotation characteristics of hematite,' goethite,2 and quartz3 have demonstrated the electrical nature of the interaction of the collector with these oxide surfaces; anionic collectors are effective on positively charged surfaces and cationic collectors on negatively charged surfaces. Thus, from the differences in the electrokinetic properties of the above-named oxides, a theoretical basis has been provided for their separation by some typical collectors. Examination of the results reported for hematite and goethite shows that their electrokinetic properties and flotation characteristics are remarkably similar. It is of considerable interest, therefore, to examine similar information for magnetite, another common iron oxide, in order to consolidate the flotation characteristics of the three principal minerals of oxide iron ores. Such information is practically significant in the up-grading of both natural and artificial mag- netite produced from taconite, and in the treatment of partially oxidized magnetite ores. Information on maghemite and lepidocrocite, polymorphs of hematite, and goethite, respectively, is also of some theoretical interest in ascertaining the effects of crystal structure and of hydration in the iron oxide group. This article reports the findings on the general flotation characttxistics of magnetite, and compares the results with those obtained for other iron oxides. Experimentally, tlhe surface properties of magnetite were investigated by electrophoresis, and by measurement of the aclsorption of some typical flotation collectors. Its flotation behavior was tested by contact angle measurements and by simple flotation tests using a modified Hallimond tube. The basic information thus gathered was shown to be directly applicable to the interpretation of the results of batch flotation tests made on an artificial mixture of magnetite and quartz. EXPERIMENTAL MATERIALS Magnetite: Magnetite concentrate from Port Henry, N. Y., was further purified by fine crushing and magnetic separaiion, and was used throughout this investigation. For flotation tests the 150/200 mesh fraction was iso1ated and was cleaned by leaching briefly with warn 0.1 N HC1 followed by repeated washing with demineralized water. The final sample analyzed 71.71 pct Fe, 22.37 pct Fe" and 0.47 pct insoluble, and was stored in demineralized water. For e1ectrophoresis and adsorption measurements, the —400 mesh fraction of the magnetite concentrate was ground dry in a pebble mill. The surface area of the ground sample, as determined by the gas permeability method, was 70,000 sq cm per g. Since artificial magnetite has been reported to possess somewhat different physical properties than those of natural magnetite, it also was briefly examined. Preliminary flotation tests on a sample of artificial magnelite, prepared by reducing Brazilian hematite in a C0/CO2 mixture and analyzing 71.94 pct Fe and 23.78 pct Fe'', gave, however, nearly identical results with those using natural magnetite. It was concluded that artificial magnetite behaves similarly to natural magnetite. Samples which had been magnetically separated showed a tendency to cluster together due to residual

Jan 1, 1962

By P. R. PaeIay, A. Slibar

Using three-dimensional, stress-deformation rate equations for a Bingham plastic, an approximate solution for the laminar flow of drilling mud between the drill pipe and casing is given for the case when the velocity gradients due to axial flow are large compared to velocity gradients due to rotation. INTRODUCTION The fact that drilling mud can be treated, to a first approximation, as a Bingham plastic has been established by several investigators12,3,4,5. A Bingham plastic is a material that is rigid until a certain combination of stresses exceeds a critical value. When the stresses are sufficiently high to initiate flow, the reduced stresses have a constant ratio to the corresponding deformation rates at each point. Prediction of pressure and torque requirements to produce the desired flow of the material have been made by analytical solutions due to Bingham6, Reiner7, and Buckingham8. One part of the present means of calculation that requires clarification is the flow between the drill pipe and casing. Present methods treat the flow resulting from the rotation of the drill pipe separate from the flow produced by the axial pressure gradient. Since the non-linear behavior of a Bingham plastic implies that solutions cannot be superposed, the present analytical investigation was undertaken to obtain a solution to the problem of combined axial and tangential flow. Equations have been proposed for the three-dimensional flow of a Bingham plastic9,10,11 and it has been shown that the proposed equations lead to the usual solutions from the one-dimensional theory". Applying these equations to the flow between two concentric cylinders the problem of axial flow only13 and tangential flow only12 have been solved. In addition to the separate problems of axial and tangential flow between concentric cylinders, the authors have determined the relationship between external torque on the inside cylinder and axial pressure gradient necessary to initiate flow". The solution given in Ref. 14 points out the complexity of the present problem. The problem considered here is the case of simultaneous axial and tangential flow. The axial flow, necessary to keep the drill bit free of removed material, results from the axial pressure gradient. Tangential flow is present since the drill pipe rotates in the hole. The solution given here is valid when the shear stresses in the drilling mud due to rotation are small compared to the shear stresses resulting from the axial flow. This case for laminar flow can be encountered in oilfield drilling. STRESS-DEFORMATION RATE EQUATIONS A detailed derivation of the equations governing the behavior of a Bingham plastic is given in Ref. 10. This section briefly outlines the physical reasoning leading to this three-dimensional formulation of the stress-deforma-tion rate law. Experiments on a certain class of materials have demonstrated the following properties: (1) when a certain combination of the stresses is below a critical value no deformation of the material occurs, (2) to a first approximation this combination of stresses is independent of the hydrostatic pressure (negative average normal stress), (3) if flow occurs the ratio of the reduced stress to the corresponding deformation rate is constant at each point of the flowing material, and (4) incom-pressibility. For the one dimensional case of shear deformation, Bingham6 formulated the governing equation as dxx, = 0 for sxx < to and µdxx = s xx = to for sxx to , . where dxx is the shear deformation rate, sxx the shear stress, to the critical shear stress, and p the slope of the sxx vs dxx curve for dxx > 0. Fig. 1 shows the behavior for pure shear between two parallel plates. Taking into account the physical properties given above and assuming the critical combination of stresses to be measured by the octahedral shear stress, the fol-lowing three-dimensional equations have been proposed.

Jan 1, 1958

By R. M. Fowler, H. L. Hamner

DURING the last 25 years, there appeared in the literature a number of papers describing equipment and operating techniques for the determination of total oxygen in iron and steel. In the early papers, comparatively little attention was paid to side reactions that occur when iron is saturated with carbon at a high temperature in a high vacuum. As more experience was gained with the new method, the limitations appeared. Metals, with a boiling point lower than iron, distilled out of the crucible, condensed in the cooler part of the furnace, and subsequently reacted with carbon monoxide to form oxides and carbon. Aluminum, manganese, and the alkaline earth metals proved troublesome in this respect. Modifications have been devised to overcome the difficulties due to aluminum and manganese, while the alkaline earth metals are not of too much concern as yet to the steel chemist. The reactions of sulphur have received less attention, although it is generally recognized that some carbon disulphide is probably formed. Liquid air traps have been used in some cases to prevent any carbon disulphide from entering the analytical train. Sulphur was not a particular problem at the Union Carbide and Carbon Research Laboratories until the analysis of the irons of higher than usual sulphur contents became necessary. In order to describe the procedure developed for such irons, it will be necessary to first describe the type of vacuum-fusion equipment employed because the operation of vacuum-fusion equipment is an art to a considerable extent. At the Laboratories, vacuum-fusion equipment has been in daily operation since about 1930. Over the years, the evolution of this apparatus has been governed by the versatility required to analyze a wide variety of materials. Since all types of materials from high purity metals to slags are analyzed and, since seldom more than a few samples of one type are analyzed in succession, the apparatus was designed for accuracy and flexibility rather than for speed. A general view of the equipment is shown in Fig. 1, while Fig. 2 shows the relationship of the various parts. In Fig. 2, A is a vertical double-glazed 24X27/8 in. OD silica tube heated with a 20 kva mercury-arc high frequency generator. The tube is closed with a water-cooled brass head attached with de Khotinsky cement. A turret cap fits on this head and is sealed with a 1/8x3 in. "0" ring. The head contains a sight glass and two 8 in. horizontal glass tubes, for sample storage, cemented in with de Khotinsky cement. B is a four-stage Gaede mercury diffusion pump connected to the water-cooled head with a 11/2 in. copper tube through a flange with an "0" ring. The output of the vacuum pump feeds into an automatic Toepler F pump which compresses the gas sample over mercury in the measuring burettes, G and H. There are bypasses in this line for a McLeod gage C and a Piranni gage D, a manometer E, and for initial pumping out of the system with a Cenco Megavac backing-up pump. The reduction crucible shown in Fig. 3 is machined of Tungar Bulb quality (A.G.K.T.E.-2) graphite. The sample is guided into the crucible with the graphite funnel depicted on this figure. The arrangement of the crucible, radiation screens, etc. in the furnace is as follows: A 1 15/16x61/2 in. Alundum thimble, porosity RA-84, with two 1/8 in. holes near the top and opposite each other which take a pair of special tongs used for lowering it in place, is prepared. A 3/4 in. layer of powdered graphite is placed in this Alundum thimble, and the graphite crucible containing 20 g of ingot iron and 0.5 g of carbon is carefully centered on this bed of graphite powder and graphite powder is packed around it to the top of the graphite cru-

Jan 1, 1953

By S. Weinig, E. S. Machlin

IN a previous study of the grain boundary stress relaxation phenomenon,&apos; the authors had arrived at the conclusion that two successive steps were involved in the complete relaxation of stress at a grain boundary. These two steps were grain boundary migration and grain boundary slip. It was further suggested that the slower of these two processes is rate controlling. In an attempt to ascertain the validity of the above, a study of grain growth kinetics on the same alloys used for the previous study was undertaken. Separate wire specimens, 0.030 in. diam, in the same as-deformed state (99 pct reduction in area) as in the previous investigation were heated to the various temperatures for a sequence of times. The compositions used and the temperatures of testing are summarized in Table I. A statistical determination of grain size was then made on each specimen, using the average length of traverse between boundaries as a measure of the grain size. Examples of typical results obtained are shown in Figs. &apos;1 and 2. The grain growth law D = ktn was found to fit most of the data. Using this relation, values of the grain growth exponent n were calculated and the inter -esting dependence of n on solute content shown in Figs. 3 and 4 was then obtained. Also, it was found that the constant K which was obtained from extrapolation is roughly independent of solute content. (K is uncertain to within ±25 pct.) An estimate of the activation energy for grain growth was made using the technique of Burke? This method utilizes the plot of the reciprocal of time necessary for the grain size to increase from a definite starting size Do, to a final size D, for each isothermal heat treatment. The slope of this curve corresponds to the heat of activation for the process. In Fig. 5 the rate of grain growth is plotted against the reciprocal of absolute temperature. The activation energies were obtained from these curves and are summarized in Fig. 6. Discussion It is interesting to note that the same saturation in the variability with concentration has been found for the grain growth exponent n in this research as was found in the previous researches on both grain boundary stress relaxationa and internal friction of dislocation origin." The significant feature is that saturation in the variation of these properties has been found to occur at about the same level of solute concentration, namely, between 0.1 and 0.5 atomic pct. The only characteristic common to these different quantities is that solute adsorption at grain boundaries and dislocation can take place and affect these values in a similar fashion. Thus, it is concluded that the grain growth exponent n depends upon solute adsorption at the grain boundaries. It appears, therefore, that theoretical considerations leading to the contrary conclusions5,6 have not treated the real process by which solute atoms exert their effect on grain growth. Prior to the analysis of the observed activation energies, certain of the aspects of the aforementioned grain boundary stress relaxation investigation will be briefly reviewed. It was found that with the addition of solute atoms the grain boundary stress relaxation peak (internal friction vs temperature) decreased in intensity. Simultaneously a second peak was observed which increased with increasing solute atoms. Both of these peaks were shown to be the result of grain boundary stress relaxation. They have been termed, respectively, poire peak and solute peak. It was suggested that the solute peak was dependent upon grain boundary migration, whereas the pure peak was a manifestation of grain boundry slip. Activation energies for both peaks were obtained as a function of Solute content. The value of the activation energy in the temperature range corresponding to the solute peak was

Jan 1, 1958

By H. W. Mead, C. E. Birchenall

SELF-DIFFUSION in pure gold has been studied by Sagrubsky,1 McKay,2 Gatos and coworkers,3,4 and Okkerse.5 Sagrubsky used a sectioning technique but reported results far lower than any of the others. The work seems to be carefully done, and it appears that a factor of 60 must have been omitted in his calculations or the units misstated by an equivalent amount. McKay used a surface activity method, and Gatos and Kurtz, following Gatos and Azzam, applied autoradiography to the measurement of activity on an oblique section through the diffusion zone. These two investigations agree well with each other but give results below those reported here. Okkerse employed a very careful sectioning technique. Chemical interdiffusion in Au-Ag alloys has been measured under several concentration conditions. Average values of the diffusion coefficient for the range of 0 to 18 atomic pct Au were obtained by Braune.6 since the diffusion coefficient probably varies markedly over this range, the values may not be too useful. Also, a plot of these data suggests that grain boundary contributions may have been appreciable at the lowest temperature employed. Ebert and Trommsdorf7 give average values for 0 to 9 atomic pct Ag, and Johnson8 reports average values for 45 to 55 atomic pct Au. Johnson also measured silver and gold self-diffusion coefficients in 49.2 atomic pct Au alloys, and self-diffusion in pure silver. The self-diffusion of gold in pure silver has been determined by Jaumot and Sawatsky.10 Other measurements which do not cover a range of temperature or are of low precision are not mentioned in this account since a review by Kubaschewski is available." This contribution reports diffusion coefficients for self-diffusion in gold, self-diffusion of gold in Au-Ag alloys, and chemical diffusion in Au-Ag alloys. Although it had been intended to obtain silver self-diffusion data in the alloys it now appears unlikely that these measurements can be done soon, so a table has been worked out for a self-consistent scheme of diffusion coefficients which should not be too far from the true values. Experimental Details Experiments on pure metals were conducted using fine gold of 99.99+ pct Au and silver of the same purity. Alloys were prepared by melting the two metals together in a graphite crucible in vacuo and allowing the slug to solidify in the crucible. After machining to a cylinder about 0.85 in. diam each slug formed one half of a diffusion couple. Compositions were determined later by analyzing chips taken from the extremities of the diffusion zones. The gold used in the preparation of alloys was sometimes pure gold but was normally either in the form of clean pickled alloy from previous experiments or gold recovered by oxalic acid precipitation from warm aqueous solution. Chips from the various stages of experimentation were dissolved in aqua regia and the solution taken to low bulk, diluted with water, and again taken to low bulk before diluting for the precipitation. This precipitated gold contained a small amount of silver as the only impurity detectable by spectrographic analysis. Disks for use in diffusion couples had opposite plane faces abraded on emery paper as far as zero grit, were annealed for 12 hr at 900°C in argon, and had one face of each disk polished to 000 emery paper. Radioactive gold was plated at about 2 ma per sq cm from a small volume of cyanide solution containing 1 mg of inactive gold as a carrier. Specimens , were freshly abraded on 4/0 emery paper immediately prior to plating. In the case of the active couples disks of a similarly prepared but unplated alloy or pure metal were placed on top and welded to the active disk. With the concentration couples disks of different compositions were welded. Welding was performed after a pressure of 5,000 lb had been applied at

Jan 1, 1958

By G. E. Pralle

INTRODUCTION The decade from 1969 to 1979 saw the crest of a wave of investments by companies and investors, primarily from the major industrial nations, in the metals and minerals industries of the so-called lesser developed countries. This was brought about by two major considerations: 1). The higher ore grades and therefore the higher profit potential of the mineral deposits in the third world countries, and 2). The desire, particularly by the European countries and by Japan, to ensure a safe supply of raw materials not available in their own countries. The decade began with the start of the Toquepala mine in Peru and the major investments in the Bougainville mine in Papua New Guinea and the Ertsberg mine in Indonesia. It ended with the start-up of Southern Peru Copper Company (SPCC) Cuajone mine in Peru and Inco&apos;s Soroako mine in Indonesia and the investments in several major alumina or aluminum projects in Australia and Brazil. Concurrent with this huge flow of funds into the mineral resources industry of the developing world was the build-up of a psychological fear in the host countries of exploitation/domination by the foreign investors. This resulted in an increasing trend towards: 1). Nationalization of existing mineral ventures, and 2). Tougher legal/fiscal frameworks for new ones. NATIONALIZATION Nationalization appeared in its earliest form as "Mexicanization" of the petroleum industry in Mexico in the 1930&apos;s, followed later by Mexicanization of the mining industry in general. This was enacted with the Mexican Mining Law of 1961 which required that 51% of the equity be owned by Mexican nationals. Later in the decade the equity share for foreign investors was reduced to 33 1/3% for the developers of the Frasch sulphur operations in the Isthumus of Tehuantepec. However, the law was not fully implemented in the copper industry until late 1970 with the purchase of 51% of the ownership in the Cananea Mining Company. The trend toward nationalization of the copper industry progressed to Chile where in 1967 under the Government of Eduardo Frei the major North American copper companies were induced to sell a one-half interest in their Chilean mines to the State. Likewise, in 1970, "Zambianization" took place, when the two major operating companies Roan Selection Trust (Amax) and Zamanglo (Anglo American) were restructured into Roan Consolidated Mines (RCM) and Nchanga Consolidated Mines (NCCM) providing the government with 51% of the equity ownership. Whilst the earlier forms of nationalization in general constituted a fairly priced buy-out (El Teniente, Chile for US$80 million, RCM for US$117.8 million, NCCM for US$178.7 million), the total nationalization of the Chilean mining companies in 1970 under Salvador Allende did not. Later, "Western" countries joined this trend and on October 29, 1973, Mr. Gough Whitlam proclaimed that "overseas capital must continue... in partnership with Australian capital" and "in some special energy cases we have an objective of 100% Australian ownership". In 1974 Mr. Pierre Trudeau stated: "The Liberal Party of Canada sets as an objective that new resources projects in the natural resource field should have at least 50% and preferably 60% Canadian equity ownership". FOREIGN INVESTMENT The situation for the foreign investor in the worldwide resource industry rapidly deteriorated from then on. New features appeared in mineral exploitation and operating agreements, centering not only on local government/local companies ownership but also on increased taxation. The new tax rate (mineral tax, royalty, and income tax) for the semi-government companies NCCM and RCM in Zambia became an effective 73%. Likewise the much publicized and discussed renegotiated Bougainville agreement brought dramatic increases in the total "take" by the PNG Government. More innovative forms of indirect taxation made their appearance and were added to the normal tax burdens of the mineral industry which already

Jan 1, 1985

By W. W. Mein

IN March 1949 the Calaveras Cement Co. was sued by five landowners whose properties are located in the vicinity of the plant. These landowners—all of them cattle ranchers—sued for dust damages of $120,338 and for an injunction preventing the company from casting dust upon their properties in injurious quantities. The issue was split, the jury deciding the amount of damages and the court handling the injunction features. The action came to trial before a jury in April of that year and resulted in damages being awarded in the amount of $7,508. A month later the court issued its injunction requiring recovery of stack dust to an 87 pct minimum. The Calaveras plant, shown in Fig. 1, is located three miles from San Andreas in the heart of the Mother Lode country, about 45 miles east of Stockton, Calif. Since it is in a small town, the company&apos;s responsibilities to its employees and to the community are different from those of plants located in large centers of population. Construction of the plant was begun in 1925, and production was started the following year. Standard gray Portland cement as well as several specialty cements are produced. Production facilities have been continually enlarged so that the present capacity is more than double what it was 25 years, ago. The most important item in the company&apos;s expansion program was the purchase in 1945 of an 11 ft 3 in. x 360 ft Allis-Chalmers kiln which had been declared surplus by the Defense Plant Corp. The company is now able to produce about 2,500,000 bbl of cement a year, and employment at the plant is approximately 300. The production of cement has always involved a dust problem, solution of which has been attempted in a number of different ways. By far the most efficient method of catching dust discharge is electric precipitation. Soon after the company went into production in the 1920&apos;s, the landowners near the plant began complaining about dust discharge. The company settled the matter by paying them a total of $27,000 for dust damages incurred during the period from 1929 to 1938. In the latter year the two-unit Cot-trell Electric Precipitator shown in Fig. 2 was installed and collected over 85 pct of the dust resulting from operation of the two 11 ft 3 in. x 10 ft x 240 in. kilns. From 1938 until 1946 the landowners registered no objection and were apparently satisfied with that dust recovery. In 1946, however, the substantially higher production resulting from operation of the new kiln immediately overtaxed the facilities of the existing two-unit precipitator. In a short time claims for dust damages were again received from the landowners. The company informed them that because of postwar shortages it would take several years to install a new precipitator. The company stated that it intended to purchase an additional precipitator and offered in the meanwhile to pay the landowners a fair amount to cover their damages. This offer was rejected and the landowners filed suit in the Superior Court of Calaveras County asking for total damages of $120,-338 and for the injunction outlined above. Case for the Ranchers The attorneys for the plaintiffs produced three different types of witnesses: first, the landowners themselves and members of their families; second, other cattle raisers who were sympathetic to the plaintiffs; and third, several types of technical experts: veterinarians, soil chemists, and an aerial photographer. The testimony of these witnesses was designed to establish that the flue dust from the plant had not only damaged the land and the forage, but had also caused fluorine poisoning to their animals. By a combination of these causes, the plaintiffs attempted to prove substantial loss of profits.

Jan 1, 1952

By P. T. Carter, A. B. Murad, H. B. Bell

The distribution of manganese and oxygen between molten iron and FeO-MnO-SiO2 slags not saturated with SiO2 has been determined and used to calculate activities of MnO and SiO2 in MnO-SiO2 slags. These were found to be intermediate between the corresponding activities in FeO-SiO2 and CaO-SiO2 slags. THE equilibrium constant for the reaction between molten iron containing manganese and slags containing FeO and MnO, namely: FeO(slag) + Mn = MnO (slag) + Fe(1iquid) is most conveniently represented by: (MnO) Kmn== (FeOHMn] [Fe] is omitted, since for dilute solutions of manganese in iron, afe is approximately constant. When activities are used for (MnO), (FeO) and [Mn], Kmn is a true equilibrium constant and will apply to all types of slags, but when weight percentages are used, the values obtained for Kmn for different slags vary considerably. The equilibrium between iron containing manganese and relatively pure FeO-MnO slags has been investigated by several workers;1-4 the most recent investigation reported is that of Chipman, Gero, and Winkler.4 Their results, corresponding to slags containing up to 4 pct SiO2, were represented by the equation: 6440 log KMn = +2.95 In this case both slag and metal may be assumed to be ideal solutions, therefore the values of Kmn so derived represent the true constant for the manganese reaction. As the molecular weights of MnO and FeO are almost equal, weight concentration of these oxides may also be used in the above expression. Acidic oxides such as SiO2 and P2O5 affect the activities of FeO and MnO differently, so that when total concentrations by weight of FeO and MnO are used in the above expression for Kmn the values obtained are no longer constant. These will be denoted by K&apos;mn. Körber and Oelsen5 investigated the manganese reaction using silica-saturated iron-manganese-silicate slags and found: 7940 logK&apos;mn =3.172 This corresponds to Kmn values much higher than those obtained for pure oxide slags. The results of Körber and Oelsen, and Chipman, Gero, and Winkler are summarized in Table I. In the present investigation it was decided to study the manganese reaction using iron-manganese-silicate slags not saturated with silica, and which fell mainly between the orthosilicate join 2FeO . SiO2 - 2MnO.SiO2 and the FeO-MnO side of the ternary system FeO-MnO-SiO2. It has been shown" that the phases present in solidified slags of this part of the diagram are (FeO, MnO) and (2Fe0.Si02, 2Mn0-SiO,) solid solutions. Such an investigation would be of interest in deoxidation and also gives information on activities in liquid slags. This equilibrium has not as yet been investigated successfully. Hilty and Crafts7 attempted to examine this reaction in a rotating crucible furnace, but were unable to obtain suitable slag samples. In the present investigation one series of experiments was carried out in a rotating crucible furnace, because the success of Taylor and Chipman8 with such a furnace in their study of oxygen distribution between molten iron and (CaO, MgO) — FeO-Si0, slags suggested that it would minimize contamination of the slag by the crucible material. A second series was carried out using a wire-wound resistance furnace. Rotating Crucible Furnace Experiments In all cases the metallic charge consisted of 800 to 1000 g Armco iron containing 0.02 pct C, 0.03 pct Mn, and traces of Si. Manganese and silicon additions consisted of electrolytic manganese (99.9 pct)

Jan 1, 1953

By Robert E. Brand, Strathmore R. B. Cooke

For a study of the bonding that occurs in magnetite pellets during oxidation, cubes of magnetite, hematite, and quartz were prepared, each with one surface polished and nearly optically plane. These faces were fired together under pressure and at various temperatures to determine whether bonding would occur. Sections of surfaces that bonded were examined microscopically. An attempt was made to measure the strength effected by this treatment. EARLIER work1,2 has shown that the strength developed by fired magnetite pellets containing silica or silicates is due to three separate effects. Two of these are associated with the formation of slag in the interior of each pellet at temperatures above 1000°C, where the atmosphere is substantially though temporarily neutral. The third is independent of the silica content and is responsible for the development of a hard shell around the pellet during the initial stages of firing, a condition which permits the pellet to assume the increasing load of the overlying burden and prevents extrusion of the slagged and semi-liquid interior. Pellets made from hematite concentrates do not show these effects unless specific additives are incorporated, and it is these differences in behavior which in large part account for the difficulty in producing satisfactory pellets from such concentrates. Elsewhere it has been stated that "the most important factor responsible for the development of strength in fired magnetite pellets containing no additive is the oxidation of magnetite to hematite and the subsequent recrystallization and grain growth of this constituent."&apos; The object of the investigation reported in the present paper was to study in detail the mechanism described above and to evaluate its contribution to the strength of the fired pellet compared with other possible mechanisms, excluding slag bonding. This was effected by placing together polished faces of two cubes prepared from specific minerals and then heating them under constant pressure at different temperatures both in air and in nitrogen. The materials used were magnetite, hematite, and quartz. The magnetite was coarsely crystalline material from western Montana, the hematite was Itabira ore from Brazil, and the quartz was of optical grade but of unknown origin. A high-grade Lebanon (Pennsylvania) magnetite concentrate was used to prepare briquets for the investigation of bonding strength. Analyses of the iron oxide materials are given in Table I. The specimens for furnace treatment were prepared with a carborundum cut-off wheel, which cut the minerals into cubes approximating % in. along each edge. Care was taken to make the sides as parallel as possible. The edges of the faces to be polished were beveled, and the cubes were mounted in brass rings with sealing wax, this being essential to prevent the specimens from rocking during polishing. To prevent excessive friction, the wax was recessed so that only the brass ring and the face of each specimen would be in contact with the polishing lap. Each specimen was then ground with No. 600 carborundum to produce a level surface before polishing. The Graton-Vanderwilt process was not used for polishing because of the long time required by this method, but several other methods were tried. Cloth laps using levigated alumina or chromium oxide did not produce the desired polish. Satisfactory results were obtained by means of a pitch lap: which was used for all the mineral cubes, with levigated alumina as the polishing medium. The lap was operated in a machine similar to those used in the preparation of single optical surfaces. It was run at low speeds and moderate pressures, and polishing was stopped occasionally to prevent overheating of the lap. A good polish with flat surfaces could be obtained in about 5 min. After polishing the sealing wax was removed either in hot water or in a solvent such as turpentine.

Jan 1, 1955

By A. W. Schlechten, C. M. Hsiao

The apparent vapor pressures of a number of metal sulphides were determined by measuring their rate of weight loss when they were heated under vacuum. The calculated pressures are due in some instances to the volatility of the sulphide and in others to the decomposition pressure. FIE direct reduction of metallic sulphides, as in the precipitation method for lead or antimony, is not a widely used process today. However, it might be employed for the production of a number of metals if the operation were carried out under reduced pressures. Two general procedures are possible; the reducing agent could form a stable nonvolatile sulphide from which the valuable metal could be removed by volatilization or liquation. The other approach would be to choose a reducing agent which would form a sulphide that could be volatilized away from the valuable metal. A vacuum operation would serve to protect the sulphides and metals from oxidation and would increase the evaporation rates. A related process is the separation of metallic sulphides by selective volatilization either at atmospheric pressure or under vacuum. This procedure is already used commercially for the elimination of lead and cadmium as PbS and CdS from zinc calcines; it might well have other applications. To predict such processes it is necessary to know the relative volatilities of the metallic sulphides and to know whether they volatilize as sulphides or whether the predominant weight loss is due to decomposition. Such data would also be of value in studying problems such as the use of sulphides for refractories, as described by Brewer,] or in the evaluation of the theory of ore deposition from the vapor state, as proposed by Brown.&apos; Qualitative statements concerning the volatility of metallic sulphides can be found frequently in the literature and are well summarized by Mellor, but accurate determinations of rates of evaporation or vapor pressures are very scarce. Kelly" lists vapor pressure data only for PbS; his reference being to the work of Schenck and Albers,4 who measured the vapor pressure of PbS by a dynamic method between 850" and 995°C. More recently Veselovskii5 has determined the vapor pressures of the sulphides of antimony, lead, cadmium, and zinc at temperatures ranging from 360" to 1000°C using Knudsen&apos;s method. A second Russian worker, Pogorelyi,6 determined the vapor pressures of CdS and ZnS at temperatures from 900" to 1250°C. The results obtained by these workers are shown in subsequent graphs in comparison with the data of this paper. Brewer and coworkers1 have studied some of the metallic sulphides to determine their suitability as refractories in vacuum. Veselovskii&apos;s determinations on PbS checked well with those of Schenck and Albers, and his determinations of CdS check almost exactly with Pogo-relyi. For the vapor pressure of ZnS the data of Veselovskii and that of Pogorelyi are in fair agreement, as shown in Fig. 1, but it should be pointed out that Lumsden7 has discovered that the equation given by Veselovskii for the vapor pressure of ZnS: - 14,200 log P9.495 is in error by a factor of ten when compared to the experimental data. In contrast with the scarcity of data on vapor pressures, the decomposition pressures of many metal sulphides have been determined and are summarized by Smithells.8 Theoretical Considerations The experiments described in this paper consisted of determinations of the rate of weight loss of certain metallic sulphides under very low pressures at different temperatures. These data plus observation and analyses of the products reveal the mechanism of the weight loss and also provide a basis for the calculation of the vapor pressure or apparent vapor pressures of the sulphides.

Jan 1, 1953

By R. Schuhmann

D. W. Fuerstenau (Associate Professor of Metallurgy, Dept. of Mineral Technology, University of California, Berkeley, Calif.) In his excellent paper, Dr. Schuhmann has proposed a mechanism for conlrninution which can be utilized to explain a number of phenomena which have been observed in the size reduction of solids. The difference between the product obtained from a ball mill and from a rod mill can readily be explained by Dr. Schuhmann&apos;s hypothesis. Consider that the size distribution of the product from each comminution event is given by y; - 100 (x/ki) (1) where Yi is the cumulative percent finer than size x, ki is the size modulus, and is the distribution modulus for the single comminution event. The total product from a cornminution operation will be the summation of the products from all of the individual cornrninution events. If the size moduli from the various comminution events range from kl to kn , the size distribution of the total product will be a straight line on a log-log plot only to a particle size equal to k ,. Considering 100 volurnes of feed, the value of y for x equal to kl is Riven by where y is the cumulative percent finer than size kj, z is the number of comminution events of kind i, and vi is the volume of each particle crushed. y=z1 qv1+z2 qv2 (k1/k2) +.............zn qvn (k1/kn) (3) F or particle sizes greater than k1 7 e. 6. x = k3, the value of y will be given by k3 A y = z1 qv1 + z2bv2 + Z3uV3 + zn zn qvn (k3/kn)(4) Only when x is equal to k, will y equal 100. &apos;Thus, the total product from a comminution operation will be a straight line on a log-log plot strictly up to a particle size equal to kl and above that size the line will curve so that y will equal 100 for the coarsest particle or k, (see Fig. 1). The actual shape of the size of distribution curve will depend upon the relative number of conmninution events of different kinds. In the case of ball milling, the ratio kn/kl may be pite large and there will be considerable deviation at the coarse sizes in a Schuhmann plot. kIowever, the grinding action in a rod mill is such that fine particles are protected from the rods by the coarse particles. Consequently, kn/kl will be quite small and the product from a rod mill will give a straight line Schuhmann plot almost to y equal 100%. In his paper, Dr. Schuhmann also has presented a very straightforward definition of grindability derived from the basic energy equation E = Ak-a (5) where E is the energy required to comminute a material to a size modulus of k and A is a constant. According to Dr. Schuhmann, the grindability of a material is the volume of material comminuted finer than unit size per unit of energy expended, this being 1/A. For comparison of grindabilities at any size two numbers are required, both = and 1/A, and anyone tabulating grindabilities should give both of these numbers. Concerning the experimental determination of grindabilities, if the material being comminuted possesses distinct cleavage, the energy re quired for comminution is given by E = Ak-(a-y) (6) where y is small number less than = . Because of cleavage, less energy will be required for comminution. To be certain that cleavage does not affect the gindability of the material being tested, it is suggested that the method used by Dr. Charles for determining grindability be used to ascertain if the deviation exponent y is zero or finite. R. Schuhmann, Jr. (Author&apos;s Reply) Dr. Fuerstenau&apos;s interesting comparison of rod milling and ball milling

Jan 1, 1961

By J. Fageant, W. C. Ellis

All major regions in a progressively solidified germanium ingot were related through successive orders of octahedral twinning. The occurrence of lineage structure and the generation and survival of orientations are discussed. WHEN metals solidify in a temperature gradient a preferred orientation, or casting texture, usually develops. For example, in face-centered and body-centered cubic metals, most of the solidifying crystals have a cube axis, <loo>, aligned approximately in the freezing direction.&apos; In the solidification of diamond cubic metals this is not the case, since there is a natural tendency to form twin orientations.&apos; . In this paper, twinning relationships in cast germanium are described; some conclusions with respect to nucleation and survival of new orientations are discussed. In the first experiment, an ingot of high purity germanium, % in. in diameter and 1 % in. in length, was formed by progressive solidification4 from the bottom. The ingot was cut into 21 slices, each circular and about 0.030 in. thick. The top surface of each slice was polished and etched to reveal the regions of different orientations. Orientations were determined by the Laue X-ray back-reflection method. The uncertainty in the determined orientation relationships was l" or 2" when separate slices and films were involved. Frequently, however, advantage was taken of illuminating across a boundary when the patterns of the two orientations were recorded on the same film. The uncertainty then was less than 1". Often the twin relation was evident from common zones or individual reflections. Twin relationships were recognized through comparison of the values of the nine angles between cube poles of the two orientations with those calculated for successive orders of octahedral twinning. The birth and survival of each region can be reconstructed by visual examination of the etched slices shown in Fig. 1. In slice 21, where solidification began, many regions are present; these regions were found to be twin-related. Solidification appears to have started from one nucleus formed probably at the wall of the crucible.* Subsequent ori- entations were developed by nucleation on existing solid surfaces, and only in the twin relationship. This is an example of a general process of nucleation on a surface of existing solid and may be descriptively termed oriented nuc1eation.t In germanium, and other diamond cubic substances, the orienting habit is that of twinning on an octahedral plane.&apos; " The prevalence of straight traces in the polished surfaces of succeeding slices (Fig. 1) suggests that the twinning observed in the first slice persisted throughout solidification. This was confirmed by X-ray determinations. The schematic diagram of Fig. 2 shows the twinning relationships of the major regions throughout the ingot. Since all observed relationships are describable as twinning, it is reasonable to conclude that no random nucleation occurred in the freezing of the ingot. An alternative possibility would be that nucleation of a random nature occurred, but only those nuclei in twin orientations survived in subsequent growth. This is unlikely for there would be as good a reason for the growth of randomly oriented nuclei as for the growth of the many different orientations present after several orders of twinning. The many twin components contain a wide distribution of orientations, and did grow. In fact, they are the only ones found in the solid. The conditions of solidification of this ingot were such as to discourage nucleation of crystals wholly in the liquid. The rate of solidification was 0.125 in. per min. This slow rate of heat removal afforded but small opportunity for supercooling within the liquid —a condition needed to provide enough decrease in free energy for such nucleation. When nucleation occurs on an existing solid surface, the interfacial energy between the existing and forming regions is important in determining the new stable orientation. The new orientation is expected to be one which minimizes this energy. In the diamond cubic structure, the interface for the

Jan 1, 1955

By B. Ancker, E. R. Parker

The small-angle dislocation-boundary density of nickel and some of its alloys was investigated as a function of strength. It was found that the strength is a linear function of the density for pure nickel and for Ni-Ti alloys, but not for Ni-Co alloys. The results are interpreted in terms of dislocation theory. THE processes by which metals deform are still poorly understood, even though there has been a concentrated research effort in this field during the past fifteen years. Single crystals and individual grains in polycrystalline aggregates often develop a subgrain structure when deformed. Substructure formation occurs as a result of local plastic bending and its development is augmented by annealing at moderate temperatures.&apos; Investigations made to date, largely qualitative in nature, have shown that the substructure is composed of a network of small-angle boundaries. The purpose of the present paper is to present some quantitative data on substructure (obtained by X-ray techniques) and to correlate the results with the strength of the metal in which the substructure existed. Nickel and some of its alloys were used for the experiments. The presence of certain kinds of foreign atoms greatly alters the formation and effect of the substructure. Polycrystalline tensile specimens were prepared from high purity nickel, two Ni-Ti alloys, and two Ni-Co alloys; the composition of these materials is given in Table I. Tensile specimens having a reduced section 1/4 in. diam by 3 in. long were machined from materials which were refined, cast, forged, and swaged in the authors&apos; laboratories. The specimens were annealed for 1/2 hr at 1150°C, a treatment which produced grains having a diameter of approximately 0.5 mm. This rather large grain size was used to facilitate later examination of the substructure. Duplicate specimens of pure nickel and of each alloy were strained various controlled amounts in tension at room temperature and recovered for 1 hr at 800°C. (This strain induced prior to recovery will be referred to hereafter as the "prestrain.") One of each of the recovered specimens was pulled in tension at room temperature to obtain the stress-strain curves. The other bar was cross-sectioned in the gage length, carefully polished, and deeply etched to remove all cold-worked material. This specimen was then examined by the X-ray microscopic technique2 to determine the nature and magnitude of the substructure. The use of duplicate specimens permitted a direct correlation between tensile properties and substructure characteristics. X-ray microscopic studies were made with an apparatus constructed to have an average resolving power of about 4 microns. The monochromatic radiation reflected from grains which were oriented favorably was recorded on fine-grain photographic plates. These were examined at Xl00 which represents the true magnification, since there was essentially none in the X-ray system. This permitted detection of angular differences between subgrains of as little as 10 min. A very large number (over 100) of grains for each specimen was examined at this magnification and the number of substructure boundaries per grain was tabulated. An accurate relative measure was obtained under fixed experimental conditions, e.g., same grain size, resolving power, magnification, etc. The greatest source of error lay in counting the subboundaries, but this proved to be surprisingly small when repeated counts were made by different investigators. Furthermore, as the subsequent analysis indicates, whatever human error was introduced was not significant. Analysis of the Substructure Data When the number of substructure boundaries per grain was plotted against the frequency, skew (asymmetrical) distribution curves of the type shown in Fig. 1 were obtained. These are smoothed curves for the 1 atomic pct Ti in nickel alloy subjected to various prestrains and are representative of the curves obtained with all the metals. Since skew-distribution curves cannot be analyzed by elementary statistical methods, detailed investigations were undertaken in order to 1—test the consistency

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&apos;s, Allen&apos;s, or Stokes&apos;, 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