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By Robert U. King, John W. Vanderwilt

THE Climax molybdenite deposit in Lake County 100 miles southwest of Denver is located in the central part of the mineral belt extending northeasterly across the state. Principal geographic features and geology are shown on Fig. 1. The first period of molybdenite mining, which began in 1918, ended in April 1919 because of limited demand and a price drop to about 72¢ per lb. During this time the ore came from the Leal level and surface outcrops at a higher elevation. Rate of mining was 250 tpd and several million tons of ore averaging 0.7 pct molybdenite were developed. Since April 1924, when the second period* began, Climax Molybdenum Co. has been the only operating company. Production in 1924 was 400 tpd and finding ore was a continual problem. When the White tunnel was extended, however, further ore was encountered. The orebody was thought to be tabular until 1926, when B. S. Butler recognized the relation of the developed ore on the Leal and White levels to a central area of fine-grained hydrother-mal quartz, and by 1929 diamond drilling had blocked out indicated ore reserves in excess of 100 million tons. In 1946, on the basis of information obtained from 25 miles of mine workings and a completed exploratory program involving over 200,000 ft of diamond drilling, the present authors reviewed and brought up to date the geology of the orebody. More recently Sears," employing microscopic techniques, made a study of hydrothermal alteration and mineralization, and Howell and Schassberger'" restudied available geologic data. Production (1953) of molybdenite ore has been expanded to over 25,000 tpd and total production from 1918 through 1953 has been: Tungsten, tin, and pyrite are byproducts and monazite also was produced from 1949 through 1951, after which it was not saved. A maximum of 15 to 20 tons of monazite was produced. Geology of the Area Pre-Cambrian crystalline rocks constitute most of the Mosquito Range for several miles to the north, east, and south of the Climax molybdenite deposit, see Fig. 1. To the west the crystalline rocks are in fault contact with shales and sandstones of Pennsyl-vanian age. Both crystalline rocks and sediments are intruded by dikes and sills of Tertiary age. Numerous faults with small displacements are to be found in the crystalline rocks east of the Mosquito fault and in the sedimentary beds to the west. Pre-Cambrian Rocks: The pre-Cambrian rocks consist of schist and gneiss, identified with the Idaho Springs formation, and granite with minor pegmatite correlated with the Silver Plume granite of the Silver Plume area. The Idaho Springs formation is a general term applied to pre-Cambrian schist and gneiss found over a large part of the Colorado Front Range. At Climax this formation consists largely of biotite-schist and quartz-biotite gneiss with minor quantities of plagioclase and orthoclase, although in places appreciable quantities of feldspar and quartz are present in the more gneissic varieties. Locally, especially along the contact with granite, recrystal-lization of the schist has produced coarser texture and a more pronounced than average gneissic appearance. The gneiss and schist have been mapped as a single unit by Butler and Vanderwilt (1933)" and by Singewald (1951).12 Schist predominates at the higher elevations of the Mosquito Range and in the area to the north and east of Climax. The regional trend of schistosity is northeast with varying dips to the east. Silver Plume granite and associated pegmatite intrudes the Idaho Springs formation. Silver Plume granite in many places and in the Climax district in particular has an irregular form, and many large and small inclusions of schist and gneiss occur within the granite. Granite predominates at the surface in the immediate vicinity of the area of hydrothermal alteration and extends for several miles to the northeast and southeast. As more schist is present at lower levels of the mine than in the upper levels, the suggestion is that the granite is sill-like in form,

Jan 1, 1956

By C. F. Allen, G. B. Walker

The sink-float methods designated by heavy-media separation processes were pioneered by C. Erb Weunsch for the treatment of base metal ores as an improvement over jigs. The work of Weunsch was further developed by Victor Rakowsky and The American Zinc, Lead and Smelting Co. Early in the development of the processes, the inherent unsuitability of galena as the solid constituent of the medium was recognized and ferrous media amenable to magnetic recovery and control were developed. The high efficiency and low cost of magnetic recovery and cleaning of ferrous media regardless of particle size, slime contamination, or surfacial oxidation had led to the adoption of ferrous media by all of the sink-float plants operating under the heavy-media separation processes patents controlled by American Zinc, Lead and Smelting Co. Approximately 2,000,000 tons of base metal and nonmetallic minerals are treated each month by these methods. Heavy-media separation processes are a modern practical and economical adaptation of the well-known laboratory procedure for separating a mixture of two solids by immersing the mixture in a liquid having a specific gravity intermediate the specific gravities of two solids. The lighter solid floats while the heavier sinks. This method of separation has been attempted on a commercial scale, but the high loss and high cost of the organic liquids halted the development of the process. Many attempts have been made to simulate a heavy liquid by using a suspension of a finely divided solid in water. If the solid phase of the suspension is ground fine enough, the suspension can be made stable or so slow settling that a substantially uniform specific gravity can be maintained from top to bottom of the bath. However, any material separated by such methods will inevitably be contaminated by some slime which will eventually accumulate in the bath and cause a viscous medium at the expense of separating efficiency. Therefore, it is necessary to provide means for continually cleaning a portion of the medium to eliminate slime at the same rate at which it is introduced to the medium. The problem of efficiently cleaning the medium limits the minimum grain size of the solid of the suspension in the case of the Chance sand process for cleaning coal, because de-cantation is the only cleaning method available. If the sand is too fine, it will be lost along with the slime. Therefore, coarse sand must be used, and to maintain a semblance of a uniform suspension, it is necessary to use strong rising water currents. The combination results in a separation based more on hindered settling classification than on sink-float principles. As previously mentioned, galena was used as the solid constituent of the medium during the early stages of the development work. The high specific gravity of galena made it suitable for the preparation of medium for high specific gravity separations. Galena can be cleaned by either decantation or by froth flotation. As with sand, de-cantation limits the minimum particle size of the media that can be cleaned without excessive loss. Froth flotation for cleaning galena medium has been used, but the problem of floating fine galena that has been exposed to extensive oxidation is well known to be a most difficult one. Last year the largest heavy-media plant m the world, and the second plant to be installed, converted from galena medium to ferrous medium despite the fact that the ore contains galena which can be used as medium. The change to ferrous medium has been beneficial in many ways. Today all the heavy-media plants have been converted from galena to ferrous media. Unquestionably, ferrous media have the widest application of any media developed, for the following reasons: 1. Ease of recovery and cleaning by magnetic means. Particle size or surface condition not a factor. 2. Low consumption per ton of ore treated. 3. Resistance to abrasion. 4. Widest range of media densities, including higher workable densities (1.25 to 3.4) than have been found possible with nonferrous media. 5. Space required for recovery and cleaning of ferrous media is considerably less than that for nonferrous media. 6. Ferrous media require lower capital investment and operating costs for media recovery and cleaning. Advantages of Heavy-media Separation Processes Heavy-media separation processes offer the following positive advantages, amply demonstrated on a wide variety

Jan 1, 1950

By S. J. Burns, W. W. Webb

The dislocation arrangements formed during unsteady propagation of cleavage fractures on (010) planes in LiF have been investigated by high-resolution etch-pit techniques and by X-ray diffraction topogvaphy. In impurity-hardened crystals, cracks propagating in any direction on (010) planes at velocities of about 103 cm per sec are usually accompanied by light plastic deformation which is enhanced wherever the crack is allowed to hesitate. Dislocations with [011] type Burger's vectors are often formed looped around the crack tip. They are dragged along with the crack tips leaving edge dislocations lying nearly parallel with the clearage surface about 5µ from it. These dislocations are easily overlooked since they may initially intersect with the cleavage surface infrequently and later may disappear from the crystals due to image forces during aging at room temperature. Although the plastic work associated with these dislocations is only comparable with the reversible (010) surface energy, an instability in crack propagation appears due to a limit of the velocity with which dislocations can be dragged along with the crack. Transition to a fully brittle nonplastic fracture mode occurs when the crack velocity exceeds the velocity with which dislocations can be moved by the stress field of the crack. TRANSITIONS between brittle and ductile modes of fracture appear to be common processes in the behavior of materials in which the flow stress is close to the stress at which brittle cracks can propagate. High-strength engineering alloys fit into this category and the transition from ductile to brittle modes of crack propagation may be associated with catastrophic failures in these important materials. The methods of theoretical mechanics indicate the geometrical conditions in which these processes may occur but the detailed mechanisms controlling the generation of dislocations in the initiation of the plastic mode and the process by which the loss of plasticity occurs on transition to the brittle mode are not yet clear. Since these mechanisms are not amenable to direct observation in engineering alloys we have chosen a semi-ductile alkali halide LiF as a model system in which to observe transition mechanisms between plastic and brittle modes of crack propagation. Cleavage cracks in this system are known to undergo a plastic-elastic transition at velocities between 103 to 104 cm per secl and dislocation configurations in LiF are amenable to study by optical-microscopic observation of dislocation etch pits2 and by X-ray diffraction topography.3 We have been able to identify a dislocation mechanism responsible for the transition from brittle to slightly plastic modes of crack propagation in LiF. A model based on this mechanism permits calculation of the critical crack-propagation velocity for this transition and indicates the importance of the stress dependence of dislocation velocity in determining the critical crack velocity. Of course, this model cannot be carried directly over to more complex materials but it is quite possible that its qualitative features are generally applicable. Dislocations intersecting fresh cleavage surfaces in LiF were reported by Gilman,4 by Forty,5 and by Wash-burn et a1.6 Such dislocations were construed to have been nucleated where the cleavage crack hesitated or stopped, near stress concentrators, such as cleavage steps, on the crystal face. The loci of such dislocations deposited On the cleavage plane in bands were called "stop lines" or "deformation zones". Gilman, Knudsen, and walshl measured the velocity of cleavage cracks in lithium fluoride by evaporating thin resistive strips on the crystal side and recording

Jan 1, 1967

By James K. Gluck, William E. Galloway, Gary E. Smith, John P. Morton, Christopher D. Henry

INTRODUCTION Surface mining and in situ leaching of uranium have the potential to alter ground-water quality around mines and leach sites. Of particular concern is the fate of uranium and its associated trace elements: molybdenum, arsenic, and selenium. We wish to under- stand the natural processes that control trace element concentrations in ground water and how these processes will influence dispersion of the elements from a mineralized zone, both naturally and during and after mining or restoration. For example, it is commonly recognized that the trace elements are soluble in oxidizing ground water but are insoluble, and can be precipitated, in reducing ground water. Thus oxidizing, metal-bearing water leaving a deposit could re- enter reduced ground, causing the water to be re- reduced and the trace elements to be, reprecipitated. In a sense, this is recreating the original mineralization process. To accomplish the above goals, we have (1) examined the theoretical controls of concentrations based on the available geochemical and thermodynamic data, (2) determined the major ion composition and oxidation-reduction status of Oakville waters because of the influence of these factors on trace element solubility, and (3) determined trace element concentrations and distribution in Oakville ground water. The last approach is used to evaluate how well actual behavior follows predicted behavior. This report focuses on two elements, uranium and molybdenum, because they exemplify the results obtained. The report also is restricted to a regional study of Oakville ground water. Results of more de- tailed study in and around major uranium districts in the Oakville and much of the raw data that support the conclusions in this report are presented in Galloway, Henry and Smith (1980). This report is part of that larger study, which concerned the depositional systems, hydrology, and geochemistry of the Oakville. The U.S. Environmental Protection Agency funded the study, under grant numbers R-805357-01 and R-805357-02. Theoretical controls were determined by reviewing the available literature on aqueous chemistry and behavior of uranium and molybdenum. To aid in under- standing water chemistry, Oakville water analyses were run through a modified version of the computer model WATEQF (Plumer, Jones, and Truesdell, 1976). WATEQF calculates speciation of dissolved ions and determines saturation with respect to a variety of minerals. In the discussion below, ion activity products (IAP) are compared with the equilibrium constant (KT) for various reactions and mineral products. Values of log IAP/KT near zero indicate that the water is in equilibrium with a mineral. Values less than -1 indicate considerable undersaturation and values greater than +1 indicate oversaturation. Galloway, Henry, and Smith (1980) give a more complete discussion of the application of this approach to Oakville water chemistry. Eh-pH diagrams have been constructed or adapted from the literature to predict what form -- dissolved ion or stable mineral species -- uranium and molybdenum assume under various conditions. Construction of the diagrams has followed procedures described by Garrels and Christ (1965). This approach is particularly appropriate because the solubility of the elements is Eh-dependent, and Eh varies greatly within the Oakville aquifer. A number of assumptions or approximations are inherent in the use of Eh-pH diagrams and chemical models such as WATEQF and in the interpretation of water chemistry in general. Both Eh-pH diagrams and chemical modeling rely entirely upon available thermo- dynamic data, including free energies of formation and dissociation constants for various reactions. These values are known to varying degrees of accuracy. Most major ions and minerals are relatively well control- led; however, data for trace metals are much poorer. Thermodynamic data are not available for some minerals, and for other minerals, two or more divergent values exist. By necessity, we have relied on the judgment of others to evaluate thermodynamic data. Calculations by WATEQF and constructions of Eh-pH diagrams are based on an assumption of equi1ibrium. Equilibrium may not be comnon in low-temperature aqueous environments; at best, ground-water composi tion may be in a state of dynamic equilibrium, continuously changing due to changes in environmental conditions. Eh-pH diagrams show what phases are stable at equilibrium under given conditions; they do not prove that the phases actually exist. Many minerals persist or form metastably under conditions outside their equilibrium stability field. The kinetics of reactions, which cannot be evaluated here, are important in determining what phases occur. Kinetics may be less of a problem for ground water that travels and evolves slowly through a semihomogeneous matrix than for many other natural systems. Eh-pH diagrams show equilibrium fields only of phases included. They do not indicate anything about stability relative to phases not included in the diagram. WATEQF, obviously, cannot calculate the degree of saturation of a mineral not included in the program or for which the appropriate ions were not analyzed. Thus, a mineral that was not considered may be the most stable phase under a given set of conditions and may control the solubility of a trace element. Also, this study is limited exclusively to in- organic compounds. Organic material is known to be an

Jan 1, 1980

By W. R. Kanne, P. R. Strutt, R. A. Dodd

A study has been made of the creep behavior of ß-NiAl of stoichiometric composition in the temperature range 475" to 775°C. Single crystal tensile specimens were deformed under a constant applied load. From slip line studies and tensile axis rotations it was concluded that the crystals deformed by pencil-glide on (100) and (110) planes with a (100) slip direction. Electron microscope thin-film studies showed evidence for profuse cross-slip, and the dislocation Burgers vector was determined to be (100). There was no tendency for the dislocations to lie in definite slip planes, although a strong alignment of segments of edge dislocations was frequently seen. The activation energy for creep in the temperature range 475" and 775°C was judged to be much lower than that for creep at temperatures above 775°C. It is possible that the rate-controlling process is the thermally activated cross-slip of screw dislocations. In recent years considerable interest has developed in the possible use of high-melting-point intermediate phases for high-temperature applications necessitating good creep resistance. Ordered alloys such as Ni3A1, modified by alloying additions, have received particular attention, culminating in the recent development by Pratt and Whitney of single crystal turbine blades.' The intermediate phase NiAl has considerable theoretical interest from a creep standpoint because not only is it ordered up to the melting point (-1650°C at stoichiometry) but it contains a high concentration of structural vacancies on the aluminum-rich side of stoichiometry. These vacancies are known to exert a strengthening effect under some conditions,' but in addition they might be expected to affect high-temperature creep rates through dislocation climb. The present paper deals with the slip line and dislocation structures developed during creep of stoichiometric NiAl between 475" and 775C, and with possible attendant creep mechanisms. MATERIALS AND TEST TECHNIQUES NiAl ingots of stoichiometric composition were prepared by induction melting 99.996 pct A1 and 99.98 pct Ni (kindly provided by the Kaiser Aluminum Co. and the International Nickel Co., respectively) in 100 cc pure alumina crucibles in a helium atmosphere. No chemical melting flux was used in order to avoid con- tamination of the alloy. Each ingot was slowly direc-tionally solidified to avoid porosity and to produce very large grains up to 2 in. in length. In this way, ingots were obtained which were suitable for sectioning into single crystal creep specimens. Chemical analysis indicated that all alloys were within the range 49.6 0.3 at. pct Ni. For the present investigation, identical rectangular single crystal blanks were cut vertically from one particularly large crystal in an ingot using a series of three diamond cut-off wheels with appropriate spacers. Thus, all sliced crystals had the same orientation with the tensile axis parallel to the long side of the rectangle; the initial orientation of the tensile axis is shown as S, in Fig. 1. The blanks were homogenized at 1250 to 1300°C for 48 hr and subsequently cooled slowly to room temperature. A gage length of rectangular cross section and about 0.75 in. in length was prepared on each specimen using an electrolytic lathe and a dilute nitric/phosphoric acid electrolyte. The gage length cross section was 0.250 0.0005 in. by 0.040 ± 0.0005 in. Holes to accommodate tensile grips were electrolytically machined using a rotating acid jet. After creep testing, this same technique was used to cut discs for transmission electron microscopy. Thus, all shaping was done electrolytically, the only exception being that (122) sections were spark-machined from some speci-

Jan 1, 1970

By J. C. Yannopoulos, N. J. Themelis

Ah electronic thermogravirnetric balance was used to measure the veductioiz rule o single cirpric oxide particles suspended in a stream of hydrogen. Very jzne thermocouples embedded in lie center and at the surface of the sphere recorded the variation of terw perature during reduction. In contrast to iron oxide reduction, where in most instances the rate of interface reactiokl is controlling, the heat- and mass-transfer phenotnena play a predolrinant role in the reduction of cupric oxide. The correlation of experitnental data or tnass lransfev lhrough the boundary layer at Reynolds nunlber 0-4 50 was as jollocs: ThE reduction of cupric oxide by hydrogen is represented by the equation: It is a highly exothermic reaction and the amount of heat released varies only slightly with temperature (-21,430 cal per g-mole at 400°C). Most of the published studies on this system have been conducted at temperatures in the range of 34 to 280c.l-&apos; The concensus of opinion has been that at temperatures below 200°C the reaction is preceded by an induction period during which there is very little or no reduction. The length of this period diminishes as the temperature of the reaction is increased1l5 and aseawa found that at 280°C reduction starts practically immediately when the oxide is exposed to hydrogen gas. The existence of an induction, or incubation, period has led experimenters to believe that the reduction of CuO by hydrogen is catalyzed by metallic copper.&apos; Boldurev and rmolaev found that mechanical additions of powdered copper to oxide did not affect its reduction, although metallic copper produced during the reduction seemed to have a catalytic effect. At least three other authors2&apos;5&apos;7 have reported that addition of copper had no effect on the rate of reduction. Pease and alor&apos; observed that water vapor had a strong inhibiting effect on the reduction at 1503C, but its effect was greatly diminished at 200 C. Pavlychenko and Rubinchik5 studied this reaction at 159 to 235 C and found that, once the reaction had been initiated, there was no inhibiting effect due to the introduction of water in the hydrogen stream; at temperatures above 183°C there was no inhibiting effect due to water vapor, either before or during reaction. The same authors noted that the rate of reduction was independent of pressure in the range of 200 to 700 mm Hg. aseawa investigated the kinetics of the CuO-Hz system at 160 to 280°C and estimated the apparent activation energy at 14,000 cal per g-mole. A similar value (13,500 1200 cal per g-mole) was reported by ond&apos; in the temperature range 148 to 216°C. Bond also reported that there was no incubation period and that water vapor had no inhibiting effect on reduction at temperatures above 190 C. The above studies have been conducted at temperatures below 280°C and the physical configuration of the system under investigation has not been defined adequately. However, it is well-known that the mechanism of gas-solid reactions depends on a number of in series physical and chemical rate prcesses.&apos;&apos; It is, therefore, essential to include among the experimental factors the geometry of the solid system and the mass-transport characteristics of the reducing gas. Scott studied the reduction of packed beds of cupric oxide cylinders by Hz-He streams of very low hydrogen concentrations at temperatures 400 to 600 C, pressure of 10 to 30 atm, and gas velocity from 0.18 to 5.8 ft per sec (3 < Rep < 30). The reduction rate was found to be mainly controlled by diffusion through the boundary layer and through the pores of the reduced copper phase. The following correlation was proposed: Scott in an earlier work studied the reduction of fixed beds of cupric oxide wire and found that the rate of flow of the gas stream through the bed had a controlling effect on the rate of reduction. The same mass-transfer phenomenon was observed by Bond and clark13 on a similar reduction system. The analogy between mass and heat transfer through the boundary layer which exists between a solid surface and the bulk stream stems from the similarity of the differential equations representing these phenomena

Jan 1, 1967

By S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of gold and copper in dilute Au-Cu-Sn alloys have been determined using a liquid metal solution calorimeter. The self-interaction coefficient, Au - has been calculated at constant copper concentrations and n cu has likewise been determined at constant gold contents. Good experimental agreement is obtained between the interaction coefficients and nAu Cc thus demonsbating the reliability of the measured heat values. The measured data are compared with the Predictions of certain solution models. In previous publications,1,2 the results of calori-metric investigations of dilute Ag-Au-Sn and Ag-Cu-Sn alloys have been presented. The present work on the Au-Cu-Sn system concludes a program of studies of enthalpy interaction coefficients in dilute alloys of the Group IB metals with tin. Since the definition and derivation of an enthalpy interaction coefficient has been discussed previously,1,2 no restatement of this theory will be presented here. From the determination of the partial heat of solution of gold and copper in ternary alloys of various copper and gold contents, values of the interaction coefficients can be calculated. These coefficients give an insight into the various solute interactions that occur in the liquid solutions since changes in their magnitude and sign reflect bonding changes that are taking place in alloys of varying solute contents. EXPERIMENTAL Details of the design and operation of the liquid metal solution calorimeter used in this work may be found in a paper by Poo1.3 For the present studies copper of 99.999 pct purity was supplied by American Smelting and Refining Co., gold of 99.999 pct purity by A. D. Mackay, Inc., and tin of 99.99 pct purity by Baker Chemical Co. At the commencement of each series of experimental drops, a tin solvent bath consisting of between 70 and 90 g of the pure metal was inserted in the calorimeter. The weight of the bath was accurately determined and to it were added appropriate amounts of gold or copper to give alloys of the desired composition. For determinations of approximately 0.0015 g-atom samples of Cu were used and for measurements of ?HAu approximately 0.0025 g-atom additions of Au. The heat capacity of the bath was determined at regular intervals during a series of drops using tin calibration samples. Measurements were made of the heat of solution of copper in alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of Au, respectively, in order to determine ?HCu in each alloy, and the same mole fractions of copper were used to determine equivalent values for nAu at constant copper concentrations. The composition of the bath was maintained at the desired constant gold or copper content by making calculated additions of the appropriate solute throughout the experiments. The limiting values ?HAu in alloys of constant copper content and of %c, in alloys of constant gold content were studied as a function of the mole fraction of copper or gold respectively in order to determine and nCu. Heat content and heat capacity data used in calculating values of ?ºHAu and ?HCu at the experimental temperature of 720°K were obtained from Hultgren et a1.4 &apos; RESULTS AND DISCUSSION Determinations of ?HAu. The partial heat of solution of gold in pure tin as a function of gold concentration was determined in the previous study of dilute Ag-Au-Sn alloys1 and can be represented by the least-squares expression: ?HAu(l) =-8075 + 2413xAu [l] which is valid between XAu= 0.00 and xAu = 0.05. The standard error in the constant term, which represents the partial heat of solution of gold at infinite dilution in tin,?HºAu(l)is 35 cal per g-atom, while the standard deviation of the slope, which represents n Au is ± 619 cal per- agtom. Corresponding expressions for ?HAu(l) in alloys containing constant mole fractions of 0.01, 0.02, 0.03, and 0.04 copper were obtained from the data listed in Table I and are themselves given in Table II. Fig. 1 illustrates the partial heat of solution of gold as a function of its concentration in each of the alloys. For the four alloys of constant copper concentration, the values obtained for ?HºAU(l) (in order of increasing copper content) are -8141 i 36 cal per g-atom, -8210 ± 42 cal per g-atom, -8202 ± 46 cal per g-atom and -8268 ± 51 cal per g-atom. The corresponding values of the self-interaction coefficient, n Au, for these alloys are 3103 * 644 cal per g-atom, 2425 ± 676 cal per g-atom, 2574 * 717 cal per g-atom and 2523 ± 899 cal per g-atom. In Fig. 2 these values of n Au are plotted as a function of the copper content of the alloys and are seen to remain approximately constant within the experimental limits. The addition of increasing, small amounts of copper to dilute binary Au-Sn alloys thus has no apparent effect on Au-Au interactions in these dilute liquid solutions, although more exothermic values of ?HºAu(l) do result from an increase in the copper content of the alloys. Analogous behavior was observed with additions of silver to dilute Au-Sn alloys.&apos; By

Jan 1, 1970

By O. D. Gaither

This paper is an analytical study of the flow of fluids through small vertical conduits. Small conduits are defined as 11/4-in. nominal diameter tubing size and smaller, and approximately twice this area for annular conduits (i.e., 1- X 21/2-in. annulus and smaller). Experimental data are presented for the 1-X2-in. and 11/4- X 2%-in. annuli, and the I-in. and 11/4-in. tubing, since these represent the small conduit sizes and configurations generally encountered in oilfield applications. Data have been gathered for these conduits for single-phase water, single-phase gas and two-phase water-gas mixtures, with particular emphasis on high gas-liquid ratios. Water rates in excess of 2,000 BID and gas rates in excess of 2.5 MMcf/D, and two-phase flow ratios in between these two, represent the scope of the data gathered. Existing equations have been applied to predict flowing pressures and compared with experimental data. New correlations have been developed. INTRODUCTION The increased economic pressure on the domestic oil industry in the United States has constantly required the use of new techniques and equipment designed to reduce the cost of finding and producing oil and gas. Since tangible items are most readily apparent in economic analysis, the advent of lower-cost well completions was inevitable. One of the methods used to reduce costs which has received widespread attention is the slim-hole completion technique where tubing is used as the well casing and in which small conduits are used for tubing if necessary. Small conduits, defined by Kirkpatrick1 as "11/4-in. diameter nominal tubing and smaller for tubing flow and less than twice the 11/4-in. diameter nominal tubing internal flow area for annulus flow", have also found widespread usage as siphon strings for de-watering gas wells and as "kill" strings in deep high-pressure oil and gas wells. The growing use of small-diameter tubing has resulted in an increased need for development of improved methods to measure or predict flowing bottom-hole pressures since the physical dimensions generally preclude the use of subsurface-recording pressure gauges. Even in the cases where small bombs are available, the relatively high velocities encountered at nominal flow rates make it necessary to use excessive weight bars or special hold-down devices. Attempts to use recognized correlations to accurately predict flowing or gas-lift performance in wells equipped with small conduits have been generally unsuccessful. Insufficient field data were available to allow the development of a correlation on this basis, and an experimental approach was applied in an attempt to obtain a workable relation. The experimental approach used to obtain the data presented in this paper was actually a compromise between a field installation and a laboratory study. A test well 1,000 ft in length was used to obtain flow data on single-phase liquid, single-phase gas and two-phase water-gas flowing mixtures. Liquid rates up to 2,200 B/D and gas rates up to 3 MMcf/D were used in the single-phase flow studies. Two-phase flow rates from 100 to 600 B/D with gas-liquid ratios from 500 to 8,000 cu ft/bbl were recorded. Experimental data were obtained for single- and two-phase flow through 1-in and 11/4-in. nominal tubing, and through the annuli between 1- and 2-in. and 11/4- and 2%-in. nominal tubing strings. Experimental results for the two-phase flow are compared to the Poettmann-Carpenter correlation2 which is widely used as a comparative standard for development of multiphase flow predictions in flowing and gas-lift wells. Correlations developed by Tek,3 Baxendell and Thomas" were also investigated. The experimental data recorded herein fell in between the two flow regimes as defined by Ros," and this correlation also failed to yield satisfactory results. The fact that existing correlations failed to confirm the experimental data led to the need for development of a new correlation. Although a two-phase flow study was the primary objective of this investigation, data were also recorded for single-phase flow of water and gas, and constants were developed relating to pipe roughness and equivalent diameters for annular flow. These single-phase studies assisted materially in the development of certain of the two-phase flow results. Considerable previous work has been published which presented relationship of surface measurements to bottom-hole condition. The works of Buthod and Whiteley,6 Jones,&apos; Poettmannb and the Texas Railroad Commission" are classic examples of the successful use of mathematical relationships which allow acceptable predictions of subsurface pressures, when gas is the flowing fluid. Darcy and others have derived relationships which may be used with minor modifications to predict subsurface flowing conditions in injection and water-supply wells. As previously stated, the application of the single-phase flow relationships

By C. C. Mattax, J. E. Bobek, M. O. Denekas

ABSTRACT investigations in recent years have shown that rock wettability can exert a profound influence on the displacement of oil by water from oil producing reservoirs. Core analyses frequently show oil recoveries from preferentially water-wet rock to be significantly greater than those from preferentially oil-wet rock. Thus, an accurate prediction of water-drive or waterflood oil recovery is dependent on the evaluation of reservoir rock wettability. Laboratory and field studies have been undertaken to examine and develop methods which may be used to measure rock wettahililiy, to investigate factors which may alter the wettability of reservoir rock, and to determine the wettability of specific reservoirs. It has been found that measurement of the rate and volume of spontaneous imbibition of the wet-ting phase by a rock is a reliable and reproducible test for semi-quantitarive determination of preferential rock wettability. Laboratory tests have shown that the wettability of reservoir rock may depend on both the crude oil composition and the rock type. Field and laboratory tests have indicated that coring flulids and core handling techniques can cause significant changes in the wettability of rock surfaces. However, a few fluids, brine in particular, appear not to affect core wettability and may be used when coring to determine reservoir wettability. Core handling and packing procedures have been developed which preserve core wettability during storage and laboratory testing. The wetfability characteristics of six reservoirs have been evaluated by wettabilify tests performed in the field on fresh cores cut with brine or special water-base muds. The tests indicated that all six reservoirs are water wet; however, the de-gree differed from one reservoir to another. INTRODUCTION Although surface properties of reservoir rock and interfacial characteristics of rock, crude oil, and water systems have been discussed for many years, the full significance of these properties to the production of oil is still in the process of evaluation. It is known, however, that one surface characteristic—preferential wettability of the reservoir rock—-is of paramount importance when the reservoir is being produced by water-flood or water-drive mechanisms. The importance of rock wettability has been pointed out by several authors&apos;.&apos;,%* who have found that pref- erentially water-wet cores flood more efficiently than oil-wet cores; that is, more oil is recovered from water-wet cores in the early flooding stages than from oil-wet cores. Other authors&apos;," indicate that waterflood oil recovery from cores of intermediate wettability may be greater than that from either strongly water-wet or strongly oil-wet cores. These recent investigations emphasize that the true wettability of a reservoir must be known before the performance of waterflood or water-drive reservoirs can be accurately evaluated. When reservoir wettability is to be determined by core analysis, precautions must be taken to maintain the original wettability which can be altered readily during coring5 nd testing.&apos; In the coring operation the core may be partially or completely penetrated by the drilling fluid which, if it contains surface active materials, may drastically change the wettability of the core. Also, improper core handling during stcrage and testing may change its wettability because of evaporation of fluids or exposure to oxygen or surface active contaminants. One purpose of this paper is to discuss methods for obtaining, preserving, and testing cores without altering their original wettability. In addition, the results of wettability tests on fresh and preserved cores from six reservoirs are presented where special precautions were taken to obtain samples without altering their wettability during the coring operation.

By Edgar Dunn

PART I.-DETERMINATION OF GASES IN SMELTER FLUES. IN 1907, upon arriving in Anaconda to take up work in the testing department of the Washoe Reduction Works, the. following problem was met at the car step, so to speak: complete and. exact analysis of gases, not only at the stack, but also in all departmental flues. Taken up to employ time not otherwise needed for regular testing department work, instructions were extremely liberal for a commercial plant, to the effect that accuracy should not be sacrificed to speed. In December, 1907, the work was temporarily transferred to the Great Falls Smelter, and some of the methods here given were there worked out. Differences in smelting operations at Great Falls and Anaconda, however, necessitated further investigations and the development of a new method for S03 determinations at the latter plant, where work was resumed in July, 1908, and completed about a year later. At the time of inception of the work, data (not only on percentages, but even on methods) were found to be meager in the extreme, for one or the other of two reasons: either entire lack of experiment at a large proportion of smelters, or disinclination on the part of the managements to divulge data of any description pertaining to either results or methods. In making determinations of gaseous constituents of flues, two methods are open to consideration: 1, the drawing out of a sample, and collection of the same as a whole, to be removed to the laboratory for later analysis; and 2, the absorption in situ on the flue of one certain constituent, disregarding others for the time being, or perhaps combining two or three in one determination. The first is generally the more rapid, but it is also the more inaccurate, method of analysis, even with special type absorption apparatus, being the more largely subject to error, both of reading, and also because of leakage during complicated manipulation in the laboratory. The amount used for analysis must also, because of limit of container, be small for the first method, and an average gas is very seldom obtained, necessitating for a fair average result a large number of determinations. Consequently, when we balance the time spent in a dozen determinations of short-time samples as against the time employed in making two or three long-time determinations of various constituents in situ, we are not so certain in our statement as to the relative speed of the two methods. Moreover, the method of analysis in the laboratory of 100 cc. of flue gas is satisfactory only when constituents thus determined are present in considerable quantity, results being simply approximate when determining such compounds as sulphur dioxide, sulphur trioxide, carbon monoxide and dioxide, and arsenic trioxide and water vapor, none of which are carried in all smelter flues in amounts in excess of (or even approaching) 1 per cent by volume. Special condi-

Jan 8, 1913

By Wm Price

THE object of this paper is to present a survey of some of the physical properties of sheet nickel silver when subjected to cold rolling and when annealed at temperatures extending from 350° C. throughout the commercial annealing range. A number of alloys were taken from stock and analyzed. Four of these, representing low nickel and high nickel both with and without lead, were chosen for the tests. The analyses were as follows: ALLOY COPPER, LEAD, IRON, NICKEL, MANGANESE, ZINC, PER CENT. PER CENT. PER CENT. PER CENT. PER CENT. PER CENT A 64.68 Trace 0.194 - 6.73 0.06 remainder B 65.82 1.27 0.227 6.17 0.06 remainder C 65.44 Trace 0.345 17.83 0.08 remainder D 65.60 1.08 0.238 17.77 0.06 remainder These alloys were rolled in accordance with regular mill practice to approximately No. 6 B. & S. gage. The bars (which were then coiled) were annealed together in a mill muffle and afterwards pickled in a 10 per cent. sulfuric-acid solution and cold rolled in stages of approximately .one number (B. & S.) at a time to No. 18 B. & S. gage. After each stage, suitable samples were set aside for physical tests. Additional samples were chosen for tests after the bars were rolled to Nos. 8, 10, 12, and 14 gage. These samples were annealed together in the mill muffle and, after pickling, were finished on 0.050-in. gage, yielding a series of specimens 2, 4, 6, and 8 numbers hard for the subsequent annealing tests. Tensile test pieces 9 by 1 in. (22.9 by 2.5 cm.) were cut from both lots and the central portion was milled to give a test section 2 ½ in. long by ;Z in. wide. A distance of 2 in. was marked off on the edge of each specimen with light punch marks. In the case of the annealed alloys, Erichsen test pieces 4 by 2 1/2 in. were also taken.

Jan 10, 1920

By Charles H. Grant

Some of the limiting factors relative to explosive crushing of rock and ways to overcome a few of these problems are presented. Relationships between borehole diameters, bench heights, and spacings, along with a review of the influence geometry has on energy as these are changed, are discussed. Efficiency in use of explosives and the decay of energy as it moves through rock and is absorbed and dissipated, is described, along with fragmentation as a function of spacings and energy zoning, etc. Communications are one of the major problems encountered. In an effort to provide a better understanding of the use of explosives, it is necessary to take a little different view of what explosives are, how to look at them as tools to fragment rock, and some of the problems encountered in doing so. First, take the explosive: although there are many factors involved, consider these as being reduced to only two — shock-strain imparted to the rock by the high early development of energy, and the gas effect which is a combination of heat, moles of gas formed, rate of formation of these gases which develop pressures, etc. First, consider shock energy by itself and assume there is no gas effect in the reaction. Fig. 1 illustrates a block or cube of rock, in the center of which is detonated an explosive charge which is 100% shock energy. Tensile slabbing would be seen on the surface and probably the cube of rock would generally hang together even though microcracks were formed. If the situation is reversed and an explosive whch has no shock energy and only gas effect (Fig. 2) is considered, the cube of rock would act as a pressure vessel and contain the pressure from the gas effect until it exceeded the rock-vessel strength; then the rock would break in a few large pieces. If these two kinds of energy are put together and the area of shock-strain around the explosive (Fig. 3) is considered, the two energies will be seen working together to furnish broken rock. The gas effect applies pressure to the microcracks formed from the shock energy to weaken the rock-pressure vessel and propagate these cracks to break the rock apart. It not only will be broken more finely, but will break apart at a lower pressure than the gaseffect case, since the shock energy has first weakened the rock vessel. Although tensile spalling from the shock-strain imparts momentum to the rock, the main source of displacement comes from the gas effect. The term "rock" is being used to mean any material to be blasted. These energies are absorbed by the rock in different ways. First, classify rock into two main categories: "elastic" and "plastic-acting." Elastic rock should be thought of as rock which can transmit a shock wave and is high in compressive strength, such as granite or quartzite. Since this elastic rock transmits a shock wave well, it makes good use of the shock energy from the explosive-forming cracks, etc., for the gas effect to work on. Plastic-acting rocks are rock masses which are relatively low in compressive strength and absorb shock energy at a much faster rate, thereby making poor use of the shock energy by not developing as extensive a cracked zone for the gas effect to work on. Rocks of this type are generally softer materials such as some limestones, sandstones, and porphyries. For the most part, the shockenergy part of the explosive reaction is wasted in plastic-acting rock, leaving most of the work to the gas effect. Since the ratio of gas effect to shock energy is different in different explosives, it is easy to understand why some explosives perform well in elastic rock and poorly in plastic-acting rock, and vice versa. Some of the most difficult blasting situations arise when mixtures of plastic-acting and elastic rock are encountered (Fig. 4). Fig. 4 shows an example of granite boulders cemented together with something like a decomposed quartz monzonite which is plastic-acting. The elastic granite boulders will transmit the shock-strain within itself, but when this shock tries to move through the monzonite to the next boulder, its intensity is absorbed by the monzonite and little shock-strain is placed on the adjoining boulder. In addition to this loss by absorbtion, shock reflection at the surface of the boulder will effect tensile spalling. The net effect is poor breakage of the boulders which do not have drillholes in them as they simply will be popped out with the muck. The same is true (Fig. 5) when layers and joints make

Jan 1, 1970

By M. M. Mebta, G. W. Dean, W. H. Somerton

With the advent of underground heating operations, interest has developed in the alteration of rock properties by high-temperature treatment. In the present work a number of sandstones were heated to temperatures in the range of 400°C to 800°C under both atmospheric and simulated reservoir pressures. Pertneabilities increased by at least 50 per cent and sonic velocities and breaking strerlgths decreased by an equivalent amount. Differential thermal expansion and other reactions of constituent min-era1 grains are the causes of these alterations. INTRODUCTION In the underground combustion of petroleum reservoirs, temperatures of the order of 600C are reported to have been reached in the combustion zone.&apos; At this temperature rocks are subject to extensive thermal alteration. Temperatures of this magnitude and higher may also occur in subsurface formations when subjected to bottom-hole heating, thermal drilling operations, and underground nuclear explosions. Temperatures of this magnitude might also be generated by conventional rock drilling methods at points of bit-tooth contact. In earlier work, the permanent deformation of rocks resulting from heating was reported. Major structural damage of rocks occurs due to differential thermal expansion of mineral constituents. A number of mineral alterations including crystal inversions, loss of water of crystallization and dissociation, may also contribute to changes in physical structure and properties of rock. In the present work, samples of three typical sandstones were heated to several temperatures up to a maximum of 800C and then allowed to cool to room temperature. Heating was done under both atmospheric pressure and simulated reservoir pressure conditions. Physical properties of the samples were measured before and after heating and comparisons made. Measured properties included permeability, sonic velocity, breaking strength and fracture index. Changes in physical properties were compared to changes in mineralogical characteristics as determined by thin-section. X-ray diffraction and chemical tests. EQUIPMENT AND PROCEDURE Two outcrop sandstones (Bandera and Berea) and one sub-surface sandstone (St. Peter) were selected for the tests. These samples have a wide ranee in composition and physical properties as shown in Table 1. The first series of tests was made on 2-in. diameter by 5-in. long test specimens. Test specimens used in all later work were 3/4-in. diameter by 1 1/8-in. long, this being the specimen size required for heating at simulated reservoir pressures. After careful washing, the cores were oven dried at 100 ± 5C for a minimum of 24 hours before the tests were run. Test specimens were heated in an electric furnace at a constant rate of temperature increase of 3C per minute. When maximum temperature of the run was reached, the sample was allowed to soak for one hour. The furnace was then cooled to room temperature at the same rate of 3C per minute. The entire heating operation was designed for reproducibility without subjecting the test specimens to excessive thermal shock. For samples heated under simulated reservoir pressures, a pressure cell designed by Dean was used (Fig. 1).3 The core sample was inserted into a thin-walled (0.006 to 0.01-in.) copper cup which was then mounted in a high-pressure cell. Provisions were made for the application of internal pore pressure as well as confining pressure. Tests showed that the thin-walled copper cup closed tightly around the core and satisfactorily transmitted confining pressure to the core. The core was heated by placing the entire cell into the electric furnace. The heating program was the same as that used in the atmospheric pressure runs: tempera-ture rise of 3C per minute to maximum temperature of the test, soaking at maximum temperature for one hour, and cooling at a rate of approximately 3C per minute. The cell was designed to withstand 5,000 psi at 1,000C. However, since it was considered likely that repeated heating and cooling would in time weaken the steel, 2,000 psi at 850C was set as a working limit. In the present series of tests, the pore pressure was held constant at 750 psi and the confining pressure at 1.500 psi. The pressure source was a high-pressure nitrogen tank. The two pressures were controlled manually but are accurate well within ± 50 psi.

Jan 1, 1966

By Kenneth E. Gray

The turbulent flow drag coefficients, or friction factors, have been experimentally determined for the cut-tings normally encountered in drilling operations. The gas law and average drag coefficients for characteristically flat particles (limestones and Shales) and for angular to sub-rounded particles (sandstones) were used to extend Newton&apos;s equation to a more useful form. The resulting equations are expressions for the slip velocity of a particle as a function of the particle size and shape, the bottom-hole injection Pressure, and the Bottom-hole temperature. The velocities necessary to lift actual rock cuttings as observed in the laboratory were compared with velocities predicted from the derived equations. Results indicate that there is no single correct circulating velocity and that the commonly used 3,000 ft/min linear velocity may he sufficient to lift only very mall particles. The advantage, in terms of horsepower requirements, of cycling high pressure air to obtain lower compression ratios was shown. INTRODUCTION A promising departure from standard rotary hydraulic drilling is air or gas drilling. In many instances the rate of penetration and bit life increases resulting from this method have been very substantial. Further the application of air drilling in areas of lost circulation or water sensitive pay zones has been highly successful. Purpose For the drilling contractor, the practical question remains, "How much air pressure and volume should I have?&apos; lt is necessary to have a reasonable knowledge of the air velocities and pressures required in air drilling operations for the proper design and most advantageous use of surface equipment and for adequate removal of cuttings from the borehole. Eased on experience, most operators agree that at least 3,000 ft/min linear velocity is necessary for satisfactory hole cleaning.&apos; It was the purpose of this investigation to evaluate the drag coefficients, or friction factors, for the cuttings normally encountered in drilling operations, i.e., sandstones, limestones and shales, and to utilize the values obtained to develop an expression for the minimum velocities and pressures (hence the volumes) necessary to lift these cuttings. THEORY Several investigators have done extensive work on the ability of drilling mud to lift bit cuttings. They conclude that the ability of a drilling mud to lift cuttings is dependent on the density difference between the rock being drilled and the drilling mud, the cutting size and shape, the mud flow constants, and the flow state (laminar, transitional or turbulent) of the mud. However, drilling muds are not true fluids but have a variation of viscosity with velocity in laminar flow and a constant apparent viscosity in turbulent flow. A survey of the literature revealed that no experimental work had been done to determine the velocities necessary to lift actual rock cuttings using a compressible fluid such as air or gas. In 1953, Nicolson6 stated that in air drilling fluid mechanics the particles could be assumed spherical in shape and that ; constant drag coefficient of 0.5 could be used due to the highly turbulent flow of the circulating air. By equating the turbulent resistance on the particle to the gravitational force on the particle, he obtained the expression, ^ = 2.67^y ,.......(1) where V, is slip velocity of spherical particle, ft/sec; D is particle diameter, in.; p, is particle density, 1b/ft8; and p, is fluid density, lb/ft3. However, as stated earlier, most operators seem to agree that adequate hole cleaning can be obtained by circulating a sufficient volume of air to give a linear velocity of 3,000 ft/rnin in the annular space. Basic Equation The velocity with which a solid particle freely falls through a fluid will increase until the accelerating force, gravity, is equal to the resisting forces, buoyancy due to the fluid displaced by the particle and friction due to the relative motion of the particle through the fluid. When the accelerating and resisting forces become equal,

By R. G. Davies, R. H. Richman

Several techniques, X-ray diffraction, transmission electron microscopy, conventional, metallography, and mechanical property measurements are combined to investigate decomposition in the suPersaturated solid solution Fe-27 at. pct Be. The following sequence of structures for aging temperatures below 400°C is established: massive short-range order, pseudo-FeBe (L2o) order, Fe3Be (DU3) order, sinusoidal modulation of composition, general or continuous precipitation, and discontinuous or cellular precipitation. In addition to this sequence itself, several features of the individual stages are noteworthy; for example, when coherent modulations occur, their development is parallel to (100) everywhere in the specimen apparently without incubation, and both the wavelength and the composition amplitude of the modulations increase with aging time. Two types of discontinuous reaction are observed, depending upon the aging temperature. At low temperatures (<550°C) the boundary-nucleated variety of discontinuous precipitate predominates; but at higher temperatures (>600°C) the crystallographic variety occurs instead. Hardness and flow-stress measurements clearly reflect the quoted structure sequence. Some qualitative aspects of the structure changes and of the relationship between mechanical properties and structure are discussed. BERYLLIUM in solid solution markedly strengthens iron.&apos;" A recent study demonstrated that not only were supersaturated single crystals of Fe-27 at. pct Be very strong, but they deformed primarily by mechanical twinning.3 Such behavior, coupled with the decrease in solid solubility of beryllium in a Fe from about 33 at. pct at 1165°C to about 10 at. pct at 500°C4 as shown in Fig. 1, leads naturally to questions about property changes with aging in this system. In 1929 roll,1 and later Seljesater and Rogers,5 reported that useful increases in strength could be obtained by aging quenched Fe-Be alloys, but it was not until quite recently that any of the details of precipitation in these alloys were studied. Richman6 observed that both an Fe3Be superlattice (with a DO3 crystal structure the same as Fe3A1, illustrated in Fig. 2) and a modulated structure preceded the appearance of a discrete second phase in the 20 at. pct Be composition. Here, a modulated structure refers to a periodic composition fluctuation within one crystal, while its lattice remains coherent. Subsequent work on a Fe-Be alloys by Heubner7 and von Heimendahl and Heubner8 confirmed the existence of the modulated structure, although only an FeBe (L20) ordered structure was detected (also shown in Fig. 2). Both Rich-man and Heubner corroborated the large increases in hardness during aging reported earlier, but other mechanical properties were not examined. Since modulated systems are encountered relatively infrequently, the influence of coherent modulation upon mechanical properties is not well-known. With the accumulation of information about age-hardening systems, it has become clear that many precipitation reactions cannot always be described by the concept of heterogeneous nucleation at some lattice discontinuity followed by diffusional growth. Rather, complex sequences involving prior "preparation" of the matrix are quite common; that is, a transition structure occurs in the parent phase, instead of in some "nucleus" form. Delineation of such subtle sequences appears to be a worthwhile step toward the understanding of solid-state precipitation. Since not many structural progressions of comparable nature have been reported, the objectives of the present survey are to identify and elucidate the various

Jan 1, 1967

By L. W. Pommier, F. B. Brien, A. K. Bhasin

The diflerential movement of solid particles through solid-liquid suspensions is very important to many branches of engineering. The flow of suspensions around immersed bodies is mainly of a turbulent nature. Problems are encountered when attempts are made, as is the general practice, to extrapolate the velocity and resistance relationships of Newton, pertaining to Newtonian systems, into non-Newtonian solid-liquid suspensions. The conventional velocity and resistance relationships for turbulent flow in fluids when applied to suspensions, do not take into consideration the two very important variables: suspension particle size and solid volume fraction. A study of the effect of suspension particle size (dgb) on the velocity of falling balls leads to the concept of a critical particle size (dgc) at which the suspensions will be Newtonian. This leads to the classification of static suspensions into two types: suspensions consisting of particle of diameter dgh > dgt, and those with dgh, < dgr. Separate velocity and resistance equations for these two types of suspensions have been proposed, taking into account both the solid particle size and solid volume fraction. The agreement between the velocities predicted from the proposed equations and the measured velocities, confirms their validity. The resistance force offered by suspensions to the movement of immersed bodies has been calculated from the proposed equations, and the effects of suspension particle size and solid volume fraction on the resistance force and velocity have been examined. The movement of immersed bodies in solid-liquid suspensions is of great importance in many areas of engineering such as minerals processing, oil well drilling, suspension flow in pipelines, and hydrometallurgy. A number of mineral dressing processes deal essentially with the movement of solids in suspensions—in particular, classification, thickening, filtration, ore washing, and gravity concentration—thus a study of the fluid characteristics of suspensions is of theoretical and practical interest.&apos; A rigorous analysis of the mechanisms of momentum transport of a solid-liquid system is complex indeed. The rheological properties of the suspensions deviate from those of liquids, varying, for example, with density, solid volume fraction, size and shape of the solid phase of the suspension, and with the density and viscosity of the liquid phase. The flow of suspensions around immersed bodies is mainly of a turbulent nature and hence studies of the turbulent flow characteristics of suspensions are of par- ticular importance. Problems are encountered when attempts are made to extrapolate the velocity and resistance relationships of Newton, pertaining to Newtonian systems, into non-Newtonian solid-liquid suspensions. Due to the numerous variables present in a suspension, certain limitations and assumptions become necessary in order to produce quantitative relationships for predicting their effects. The solid particle size and the solid volume fraction are two of the more important variables. By comparing the measured and calculated Newtonian velocities of falling balls in simple static suspensions, the existing velocity and resistance relationships have been modified to take these variables into account. In order to keep the study less complex, all other variables such as the characteristics of suspending liquid and shape of the particle are maintained constant. Objective The objective of the present investigation is to modify the Newtonian velocity and resistance equations in order to take into account the suspension particle size and solid volume fraction. Theory Liquids are classified on the basis of viscosity, which may be defined as the relationship between applied shear stress and resulting rate of shear.&apos; pure single-phase fluids composed of small light molecules behave as Newtonian liquids, having a single viscosity pa-

Jan 1, 1971

By J. A. Pusateri, M. A. Orehoski, N. R. Arant

Plant studies on commercial-size ingots and laboratory experiments with induction furnace heats have demonstrated that the major source of ingot cracks is associated with two conditions arising during top-pouring practice: 1—solidification during pouring, and 2—turbulence created by the impact of the stream. Methods of controlling the two factors were effective in eliminating or significantly reducing ingot cracks. BECAUSE the process of removing surface defects from hot-rolled product is so costly, the steel industry is striving constantly to develop methods of preventing, or at least decreasing, the occurrence of surface defects. Investigations have revealed steel-making and processing variables related to major surface defects, and controlling these variables has led to improvements in surface quality. However, the fundamental causes of major surface defects, such as ingot cracks, have not been determined; consequently such defects persist. At the Research and Development Laboratory of the United States Steel Corp. in Pittsburgh, a seam research program was initiated to determine the fundamental causes of certain major defects. As a part of the program, ingot cracks in killed, finegrained C1020 steel were selected for study. A cost survey indicated that, of the steels produced in sizable tonnages, carbon steels in the range of 0.18 to 0.23 pct C content require the most conditioning. Since this is particularly true of C1020, any im-provement of surface quality that might be effected from the study would be beneficial. Also, since the frequency of ingot cracks is exceedingly high for this grade, the steel would provide an excellent opportunity for a thorough study of the ingot-crack-ing problem. Why steels in this carbon range tend to exhibit more ingot cracks than do other steels was not considered in the investigation; the mechanism of ingot-crack formation was of paramount importance. Also, only the top-pouring practice was considered in the investigation, because this pouring procedure is used more extensively than others. In this study, ingot cracks are defined. as deep surface defects that sometimes are observed in an ingot prior to rolling but usually are observed during the initial stages of rolling on the primary mills. These defects may occur at any angle to the rolling direction but are most prominent in the transverse or nearly transverse direction. The appearance of ingot cracks on the rolled product varies with respect to their angle of formation and with the extent of rolling after their first occurrence. Ingot cracks are also termed "deep seams," "arrowheads," "irregular cracks," and "transverse cracks." Fig. 1 shows ingot cracks in a rolled bloom. This report summarizes: l—the exploratory investigation of commercial-size ingots; 2—the labor-atory investigations related to determining the source of ingot cracks and developing corrective methods; and 3—the plant evaluations of laboratory methods of decreasing ingot cracks. Exploration of lngot Cracks in Commercial Ingots Materials and Experimental Work: At the Du-quesne Works of the United States Steel Corp., five heats of killed, fine-grained C1020 steel were selected for the exploratory phase of the seam-research program. The heats were made by open-hearth practices that are considered most conducive to good surface quality. They were top-poured into 22x25 in. big-end-up hot-topped molds. One as-cast ingot and four other ingots rolled to the following cross-sectional sizes were set aside from each heat: 16x20 in.; 9 1/2x10 in.; 5x5 in.; and 2x2 in. The processing of the heats, from the time of charging in the open hearth furnaces to the end of the rolling operation on the primary mill, was observed carefully and recorded. The cast ingot and the four rolled ingots from each heat were examined for surface defects. The cast ingots were split longitudinally near the vertical center plane to expose the ingot structure beneath badly cracked regions. Also, a series of transverse sections was cut at about 1 in. intervals in a badly cracked area of one ingot. All sections were ground, polished, examined by sulphur printing and deep etching, and photographed. The rolled ingots

Jan 1, 1955

By William Rawles

THIS report is the first of a series planned by The Mineral Inquiry, organized by the American Institute of Mining and Metallurgical Engineers to make factual studies of the world&apos;s mineral resources in their political and international relations. The efforts of The Inquiry are directed toward filling certain notable gaps in available information, without duplication of many other investigations touching this field which are being conducted by other organizations, public and private. Much of its work is indirect-suggesting topics for study by other individuals and organizations and aiding in their planning and correlation. The present report is designed to show the nationality of the commercial control of mineral resources, in addition to the geographic distribution of production by nation-in other words, the overlapping of political and commercial control. Detailed accuracy cannot be claimed for the figures presented. For some companies division of ownership by nationality has been very difficult to ascertain, as many companies are reluctant to dis-close the extent of their holdings in other corporations, and the impossi-bility of tracing all stock ownership is obvious. Also there are frequent changes in the distribution of stock control. The percentages given rep¬resent only the participation that has been identified definitely, even though it is known in some cases with fair certainty that larger interests exist, as, for instance, American participation in foreign chromite companies. In bringing together these figures we have had the cordial co-operation of the United States Bureau of Mines, the United States Geological Survey, the Mineral Division of the Bureau of Foreign and Domestic Commerce, the Brookings Institution, and of many specialists connected with the mineral industries covered. The report does not cover the entire list of minerals. Coal, although it is, one of the most important minerals, was omitted because not more than one or two per cent of the world&apos;s production comes from mines that are owned by companies foreign to the countries where the coal is produced. Others, such as gold, are omitted because sufficient data have not yet been accumulated. It is hoped that some of these may be covered in subsequent reports. It is not our purpose here to discuss the significance of the figures sub-mitted, but only to point out the general nature of the problems on which they have a bearing.

Jan 1, 1933

By J. Philibert, A. G. Guy

Diffusion in the presence of deformation was studied by the method of vacuum dezincification of copper-rich and silver-rich solid solutions containing 7 to 30 pct Zn. The specimens were designed to permit the study of diffusion in separate portions of a given specimen characterized by strain rates ranging from essentially zero to approximately 10 sec-. No effect of deformation on diffusion was observed. BEGINNING with the work of Buffington and Cohen: interest in the question of the effect of stress or strain on diffusion has largely been concentrated on the enhancement of diffusion in specimens subjected to Continuous plastic deformation. The present research is a contribution to this limited area. However, as a preliminary to focusing attention on this special topic, it will be desirable to make a broad survey of the larger question, especially since there has been considerable foreign work in areas outside those of current interest in the United States. Since most of the topics referred to in the following section are both complex and imperfectly understood at present, it has been expedient in most instances to offer only a guide to the general nature of the work rather than a critical evaluation. PREVIOUS WORK The effect of elastic stress on diffusion has received considerable attention, especially with regard to the thermodynamic driving force for diffusion. The thermodynamic treatments have been based on the work of Gibb, Voigt, Planck, and Leontovich.&apos; Konobeevskii and Selisski6 made a first attempt at treating the problem in 1933, and Gorskii7 a few years later gave a solution applicable to single crystals as well as to polycrystalline specimens. In 1943 Konobeevski8 published treatments that have been the basis of much Russian work up to the present. For example, Aleksandrov and Lyubov used his work in explaining the velocity of lateral growth of pearlite. Early work in the United States was that of Mooradian and Norton, which showed that lattice distortion tends to be relieved before it can significantly affect the diffusion process. Druyvesteyn and Berghoutl1 observed a slight effect of elastic strain on self-diffusion in copper, while de Kazinczy12 found that both elastic and plastic deformation increased the rate of diffusion of hydrogen in steel. On the other hand, Grimes58 observed no effect of either elastic or plastic straining on the diffusion of hydrogen in nickel. High-frequency alternating stresses have been reported by various investigator s13-l5 to increase the rate of diffusion. A special form of elastic stressing is the imposition of hydrostatic pressure, a condition that is amenable to Conventional thermodvnamic analysis. Most of the experimental results in this area are consistent in showing a slight decrease in diffusion rates at high pressures.16-l8 Although Geguzinl reported a pronounced effect of relatively small pressures, Barnes and Mazey20 failed to Corroborate this finding, while Guy and Spinelli21 advanced an explanation of the phenomenon observed by Geguzin. It has been recognized that the thermodynamic treatment of diffusion phenomena in an arbitrarily stressed body is complicated by the fact that the desired state of quasi-equilibrium of the shear stresses cannot be maintained during a general diffusion process. However, attempts have been made by Meix-ner22-24 and Fasto to treat certain restricted cases, such as relaxation. FastovZ7 has also incorporated the general stress tensor into the thermodynamics of irreversible processes. The lattice strain that accompanies the formation of a solid solution has been the subject of much study,28-s0 and indirectly it has entered into many recent theories of diffusion. However, some Russian investigators31&apos;32 have taken other views of this matter and have predicted large effects on diffusion rates because of concentration stresses.o In completing this brief resume of previous work involving elastic strains and before proceeding to a consideration of the effect of continuous plastic deformation, it should be pointed out that deformation of various additional types may also influence diffusion. The effect of cold-working on subsequent diffusion has been studied directly by AndreevaS and by Schumann and Erdmann-Jesnitzer, while indirect evidence has been obtained by Miller and Guarnieri and by Vitman.38 Thermal stresses may also influence diffusion, contributions to this subject having been made by Fastovs7 and by Aleksandrov and Lyubv. The work of Johnson and Martin,o Dienes and Damask,3Band DamaskS considered the question of radiation-enhanced diffusion. In considering previous work on the subject of plastic deformation and diffusion, attention will be directed to those studies concerned primarily with diffusion rather than with its relation to Creep, e.g., the work of Dorn, or to the acceleration of diffusion -controlled reactions. Observations of the effect of

Jan 1, 1962

By M. J. Pool

The partial molar heats of solution in liquid tin of cadmium, silver, tellurium, and zinc have been measured at 655°. 700°, and 750°K by liquid-metal solution calorimetry. Silver, cadmium, and zinc are endothermic at these temperatures while tellurium is exothermic. Only the heat of solution of silver depends on composition while all four elements show a temperature-de pendent heat of solution. The heat of solution of tellurium is constant up to 0.6 g-at. pct, becomes increasingly more exothermic, and reaches a limiting value at 1 g-at. pct Te. The limiting value has been used to calculate the heat of formation of SnTe at 750°K. The heat effects associated with the dissolution of the compounds Ag2 Te, CdTe, and ZnTe in liquid tin were measured at 750°K. These values are cotnOined with the measured hat effects at 750°Kfor silver, cadmium, tellurium, and zinc to detertrline the heats of formation of the telluride compounds. Cadmium lelluride exhibits a heat of dissolution which has a compositional dependence. THERE is a considerable amount of interest in the compounds of tellurium because of their electronic properties. Both cadmium and zinc tellurides are thermoelectric materials and considerable work has been done on their electronic properties but a limited amount of data is available on their ther-modynamic properties. This work was undertaken to elucidate the heat of formation data on cadmium and zinc telluride. Since both cadmium and zinc are in Group II it seemed to be of interest to compare the values obtained for them with the heat of formation of a Group I telluride. Silver telluride was selected for this comparison. In the course of the work it was also possible to determine the heat of formation of tin telluride and therefore to make a comparison of some of the Group I, 11, and lV tellurides with the metallic elements silver, cadmium, and tin being in the same period. There is also a great deal of interest in the energetic changes which occur upon addition of solute elements to a common solvent. This investigation provided an opportunity to study the partial molar heats of solution of silver, cadmium, tellurium, and zinc in liquid tin. The partial molar heats of solution are of theoretical interest because solute-solute interactions are a minimum in dilute solutions and application of solution models is simpli- fied. In order to complete the analysis of solute-solute and solute-solvent interactions the temperature dependence of the partial molar heats of solution was also measured. MATERIALS AND EXPERIMENTAL PROCEDURE All materials were of the highest purity available. The silver, zinc, cadmium, and tellurium were obtained from American Smelting and Refining Co. and were reported to be 99.999 pct pure. The silver telluride, zinc telluride, and cadmium telluride were obtained from Atomergic Chemetals Co., a division of Gallard-Schlesinger Chemical Manufacturing Corp., and were electronic-grade material of 99.999 pct purity. Tin used for the solvent bath and for calibration was obtained from the Vulcan Manufacturing Co. and was reported as being 99.99 pct pure. The liquid-tin solution calorimeter used in this work is similar in principle to the differential twin-type calorimeter described by K1eppa.l Two of three identical calorimeter wells are used together during any set of experiments, one well being active and the other being passive. The wells are positioned 120 deg apart in an aluminum calorimeter block. Each well contains a multijunction thermopile and a Pyrex test tube to hold the liquid metal bath. Forty-eight of the thermopile junctions are distributed over the surface of each calorimeter well adjacent to the test tube and serve to integrate the heat effects occurring. The other forty-eight are next to the aluminum calorimeter block. The thermopiles for the three wells are connected differentially so that any change in temperature at the outer junctions (which will be the same for both wells because of the high conductivity of the aluminum block) will oppose for the two wells and result in no shift of the zero. The electrical output represents the true temperature difference between the two reaction vessels. A reaction occurring in the active well gives a comparison with another body of very similar thermal properties. In this way, any spurious heat effects due to slight temperature drifts within the entire calorimeter block are eliminated. The output of the differential thermopile goes to a dc amplifier with multiple ranges of from * 10 pv to 1 30 mv. The output of the amplifier is then fed into a Leeds and Northrup strip-chart recorder. The adiabatic temperature change is then calculated using the technique of Howlett, Leach, Ticknor, and ever.&apos; The aluminum calorimeter block is contained in a cylindrical furnace with main and control heaters

Jan 1, 1965