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By C. C. Nathan

Data are resented on the physical properties of five waxes obtained from fields in Texas and Louisiana in which "parafin" troubles are being experienced. The crude parafin was fractionated into three components, voluble in cold acetone, soluble in boiling acetone, and insoluble in boiling acetone. The acetone insoluble fraction was found to consist essentially of straight chain parafin hydrocarbons in the molecular weight range 525 to 700. Solubilities of the purified high molecular weight parafins were determined in a number of solvents. It was found that in hydrocarbon solvents, including crude oil, solubilities could be calculated satisfactorily by use of ideal solubility relations. In chlorinated, and oxygenated solvents, large deviations from ideal behavior were observed. These deviations could be partially correlated with the internal pressure of the solvent. INTRODUCTION A problem encountered in many producing oil fields is that of "paraffin" deposition. The problem refers to the deposition of material from the crude oil onto tubing, pumping rods, flow lines, or other material contacted by the crude. This problem has been recognized for nearly a hundred years, and numerous investigations have been reported on its causes and prevention or alleviation. One of the more comprehensive of such investigations was published by Reistle1 in 1932. A few of the salient findings of his report are briefly as follows: The term "paraffin" as used to describe this problem refers to the deposit of carbonaceous material which is not soluble or dispersible by the crude oil under the conditions where deposition occurs. The "paraffin" normally consists of high molecular weight paraffin hydrocarbons, both straight chain and branched, resins and asphaltic materials of undetermined nature, occluded oil and water, and possibly sand. In consistency, the deposit may vary from a soft, sticky material, to one which is hard and brittle. Deposits are usually black, although lighter colors are sometimes observed. Under the conditions of temperature, pressure, and crude oil composition occurring in the underground reservoir, the paraffin is in suspension or solution in the crude. As the oil flows to the surface, there is generally a reduction of temperature, pressure, and the amount of dissolved gases contained in the oil. Reduction of temperature and gas break-out were shown by Reistle to be factors causing reduced solubility of the paraffin in the crude. Thus, as the crude containing paraffin rises to the surface and flows to storage tanks at atmospheric temperature, the solubility of the paraffin may be exceeded. Deposition will begin at the point in the system where the temperature of the system falls below its cloud point, and continue as long as there is a further drop in the solution power of the crude for the paraffin. The severity of the deposition as well as the location of the bulk of the deposition, i.e., in subsurface or surface equipment, will depend on the amount of paraffin originally in the crude, the manner in which pressure and temperature of the crude

Jan 1, 1956

By Don Kay

A two year study into the effects of coal mining induced subsidence on cliff lines was undertaken by the Department of Mineral Resources with the support of a grant under the National Energy Research, Development and Demonstration Program. A new monitoring technique, using an Electronic Distance Meter and acrylic reflectors attached to the cliffs, provided safety for the surveyors and extensive and accurate three dimensional displacement data on the movement of the cliffs as they were being undermined. The study report included many graphs showing the measured vertical and horizontal displacements, differential subsidence, tilts and strains and included analysis of these movements with various parameters, such as, seam thickness, depth of cover and distances between the reflectors, longwall face and the edge of the chain pillar. Some of these graphs are presented in this paper and could be used, with caution, to predict subsidence movements around other cliff lines, after allowing for differences in geology and mining layout. A mechanism is suggested as an explanation for the observed high horizontal movements around the cliff lines. Sixteen percent of the overall lengths of cliffs that were undermined during the monitoring study fell and the contributions of various factors that appeared to influence the cliff falls are discussed. It is concluded that no single factor dominated as the major cause of the cliff falls and, often, many factors combined to cause cliff face instability.

Jan 1, 1992

By Edwin T. Myskowski, Alfred H. Hesse

THE development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly i00 per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi¬tion is accompanied by a change in volume of as much as S per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potters have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to g0 per cent Mn. is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparation of Alloys.-The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 Cu-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to ½ in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.-The tensile specimens, 0.313-in. diameter (1.25-in. gauge length), which were enclosed in evacuated Pyrex

Jan 1, 1942

By Randal J. Barnes

The nonlinear network optimization algorithm developed in this paper solves the following mine ventilation design problem: find the location and size of all fans and regulators which minimize the overall system power consumption while satisfying all physical, legal, and operational constraints. This work includes the formulation of the problem within the framework of mathematical optimization, the development of the computational theory, and the creation of an efficient solution methodology. The algorithm has been implemented on a microcomputer, and a small but representative example is included. The algorithm presented in this paper has four limitations. First, the optimization process is for a single point in time: the dynamic nature of a mine ventilation system in an evolving mine is not directly addressed. Second, the topology of the ventilation network is required input information. The mathematical algorithm does not optimize the size or location of the mine ventilation airways; however, the post optimality analysis techniques can be used to aid in topological decisions. Third, the problem is formulated using volumetric flow; thus, heat and moisture transfer are ignored. Fourth, the capital cost of ventilation equipment is not included in the formulation.

Jan 1, 1989

By J. M. Gomes

Bench-scale flotation tests were conducted on two western tactite ores to study the recovery of tungsten and zinc minerals. The investigation, which is part of the Bureau of Mines ongoing program to develop methods for beneficiating minerals and metals from domestic low-grade ores, demonstrated the feasibility of producing scheelite, sphalerite, and their bulk concentrates. Sphalerite concentrates containing 51 to 53 pet Zn and less than 0.11 pct W03 were selectively recovered prior to scheelite flotation. Zinc recovery ranged from 85 to 91 pct. Scheelite concentrates containing 17 to 25 pct W03 were then recovered from the ore; tungsten recoveries ranged from 88 to 94 pct. Bulk flotation concentrates containing 84 to 91 pct of the W03 and 87 to 95 pct of the zinc also were prepared. More than 98 pct of the W03 in a bulk concentrate containing 9 pct W03 was extracted by autoclave leaching with a soda solution. The zinc remained in the leached residue.

Jan 1, 1982

By M. Muskat

Calculations are reported on the differential sensitivity of the updip invasion of oil strata of varving permeability to the driving pressure differential. It is assumed that the water-oil interfaces advance with sharp fronts, or that the microscopic displacement efficiency is independent of rate and capillary pressure effects. It is found that, under such conditions, limitations of withdrawal rates will not greatly inhibit the "fingering" and bypassing tendency through high permeability strata unless the differential fluid head across the original oil column is of the order of or exceeds about 80 per cent of the driving pressure differential. In practice, such restrictions will be feasible only for oil reservoirs and aquifers of high permeability and dip, but may develop automatically under combined gas injection and water drive operations. INTRODUCTION A commonly expressed view regarding the intrusion of edge-waters into oil producing formations is that the geometry of such advance is rate sensitive. Specifically, it has been suggested that high rates of advance, stimulated by rapid withdrawals, will lead to "fingering" and an irregular type of invasion, whereas at low withdrawal rates the water encroachment will be more uniform. Two factors tend to support this view. One is the resultant effect of capillary pressure and gravity gradients in the displacement processes' involved in water intrusion, which are magnified at low rates of flow so as to improve the recovery efficiency. The other is the direct retarding effect of the rising water head as it advances upslope into the producing area. Capillary pressure forces give rise to a rate sensitivity of the oil recovery by water displacement in uniform strata as well as differential effects in non-uniform formations. These are basically independent of the effect of gravity and would also occur in horizontal beds or when the oil and water have the same density. Unfortunately, however, the fundamental equation describing the displacement process under the action of capillary pressures can be solved only by numerical or graphical procedures, and moreover the solutions are sensitive to the character of the capillary pressure and relative permeability curves.* On the other hand, the direct effect of gravity can be given a formal analytical solution if the simplifying assumption is introduced that the water advances with sharp fronts in the individual uniform strata. It depends on the absolute permeabilities of the water invaded zones and hence results in a rate sensitivity of the differential invasion in stratified media. Although a tieatment of this factor alone will not give a complete evaluation of the effect of rate on water intrusion in non-uniform pays, it should provide at least a semiquantitative measure of the sensitivity of "fingering" to withdrawal rate. Such a treatment will be presented in the following sections. GENERAL THEORY The basic element of the theory is the history of water advance updip in a uniform stratum (Fig. 1). In contrast to the assumption of constant flow rate, generally made in the analysis of displacement processes, we shall assume here that

Jan 1, 1951

By M. Muskat

Calculations are reported on the differential sensitivity of the updip invasion of oil strata of varving permeability to the driving pressure differential. It is assumed that the water-oil interfaces advance with sharp fronts, or that the microscopic displacement efficiency is independent of rate and capillary pressure effects. It is found that, under such conditions, limitations of withdrawal rates will not greatly inhibit the "fingering" and bypassing tendency through high permeability strata unless the differential fluid head across the original oil column is of the order of or exceeds about 80 per cent of the driving pressure differential. In practice, such restrictions will be feasible only for oil reservoirs and aquifers of high permeability and dip, but may develop automatically under combined gas injection and water drive operations. INTRODUCTION A commonly expressed view regarding the intrusion of edge-waters into oil producing formations is that the geometry of such advance is rate sensitive. Specifically, it has been suggested that high rates of advance, stimulated by rapid withdrawals, will lead to "fingering" and an irregular type of invasion, whereas at low withdrawal rates the water encroachment will be more uniform. Two factors tend to support this view. One is the resultant effect of capillary pressure and gravity gradients in the displacement processes' involved in water intrusion, which are magnified at low rates of flow so as to improve the recovery efficiency. The other is the direct retarding effect of the rising water head as it advances upslope into the producing area. Capillary pressure forces give rise to a rate sensitivity of the oil recovery by water displacement in uniform strata as well as differential effects in non-uniform formations. These are basically independent of the effect of gravity and would also occur in horizontal beds or when the oil and water have the same density. Unfortunately, however, the fundamental equation describing the displacement process under the action of capillary pressures can be solved only by numerical or graphical procedures, and moreover the solutions are sensitive to the character of the capillary pressure and relative permeability curves.* On the other hand, the direct effect of gravity can be given a formal analytical solution if the simplifying assumption is introduced that the water advances with sharp fronts in the individual uniform strata. It depends on the absolute permeabilities of the water invaded zones and hence results in a rate sensitivity of the differential invasion in stratified media. Although a tieatment of this factor alone will not give a complete evaluation of the effect of rate on water intrusion in non-uniform pays, it should provide at least a semiquantitative measure of the sensitivity of "fingering" to withdrawal rate. Such a treatment will be presented in the following sections. GENERAL THEORY The basic element of the theory is the history of water advance updip in a uniform stratum (Fig. 1). In contrast to the assumption of constant flow rate, generally made in the analysis of displacement processes, we shall assume here that

Jan 1, 1951

By F. C. Holden, R. D. Buchheit

In the course of studies made on the Ti-Cu alloy system,' particles identified visually as TiH were encountered unexpectedly in a specimen of high-purity Ti-0.8Cu alloy. The particles did not appear immediately after preparation, but following-storage in a dessicator for several days. Since the alloy had been vacuum annealed to a low hydrogen concentration (19 ppm by vacuum-fusion analysis), the appearance of the TiH particles was suspected as a surface contamination effect. A specimen of a Ti-0.8Cu alloy had been annealed 2 hr at 790°C and water quenched, to produce the single-phase equiaxed a structure. The metallo-graphic sample was ground through 600X paper, rough-polished on a high-speed wheel with a mixture of alumina and chromic acid, awLhish-polished on a slow-speed wheel. Disturbed metal layers were removed from the final surface by alternately etching with a 1 1/2 HF-3 1/2 HNO3-95 H2O solution and polishing on the slow-speed wheel with fine alumina. The final surface was swab-etched with a 1 1/2 HF-3 1/2 HNO3-95 H2O solution, rinsed in tap water, and dried in a stream of filtered air. The micro-structure, shown in Fig. 1, was composed of equiaxed a grains without any trace of second phase. After storage in a dessicator for 3 days, the appearance of small particles in the structure became evident (see Fig. 2). After 7 days of storage, the particles were more distinct, and in some grains, began to appear as elongated particles. The specimen then was etched a second time (without repolishing) to produce the structure shown in Fig. 4. On the basis of micro- structural observation, the line markings were identified as TiH; attempts to obtain diffraction patterns from the surface for positive identification were not successful. That the structure is a surface effect was demonstrated by grinding with 240X paper to remove the surface layer. The surface then was ground, polished, and etched using the procedures described previously. The same observations were made: the freshly prepared surface was devoid of any second phase, whereas the particles again appeared after several days storage. The same effect has been observed in other a-stabilized titanium alloys, including a high-purity Ti-0.20 alloy containing only 16 ppm H by analysis. The effect has not yet been observed in unalloyed titanium, nor does its appearance appear to be consistent with any particular alloy system. From these observations, it is concluded that certain a-titanium alloys are susceptible to the formation of titanium hydride at the surface of metallo-graphic specimens. The hydrogen probably is diffused into the surface from a residual film of etchant decomposition products. Estimates of the hydrogen

Jan 1, 1961

By A. L. Mular

The flotability of crushed zinc oxide pellets which were doped to produce more n-type or less n-type (more p-type) properties was studied with a Halli-mond tube. Flotation data are presented to show that the pH at which 50% recovery occurs and the collector concentration for 50% recovery depends upon the concentration of doping agent added substitu-tionally for zinc in zinc oxide. The time of sintering of pellets has a slight effect on flotation behavior. A speculative model is proposed to explain the observed behavior in light of the fact that zinc oxide is a semiconductor and has a space charge region at the surface. Experimental verification is necessary before the proposed model can be established as correct. In recent years, the attachment of flotation reagents to minerals has been shown to depend upon the behavior of an electrical double layer which exists in the liquid near the mineral-liquid interface.' Thus, a mineral placed in water will undergo a surface re-arrangement, most likely be preferential dissociation of lattice atoms or by surface adsorp-tion-desorption reactions, to form a dissociation electrical double layer with the solution. Among the many factors which influence adsorption processes, the past history of the mineral itself is one of the most important. Because of trace impurities, minerals from different localities may exhibit marked differences in flotation behavior. This is not unexpected, since investigators who have studied the detailed structure of the double layer's3 have known for some time that the impurity content of many minerals may exert strong influence on double layer variables. For this reason, their studies were usually made with minerals of high purity. The precise relationship between impurities in a mineral and double layer parameters such as capacity and electrostatic potential has been obscure. However, impurities in a semiconductor type mineral which is in contact with a solution have been recently shown to produce changes in the properties of a space charge layer which extends into the bulk of the semiconductor to a distance of one micron or more.4 The double layer is influenced by the space charge layer, whose origin is best discussed in terms of the band theory of solids. A qualitative description of the behavior of impurities in the bulk of a semiconductor, from a chemical point of view, is useful at this point. Briefly, impurities or defects (lattice vacancies, interstitials, etc.) in semiconductors such as PbS, ZnS, FeS2, Cu2S, NiS, NiO, Fe2O3, ZnO, CdS, MnO2 and many others, behave somewhat like acids or bases in water. For example, water dissociates into hydrogen and hydroxyl ions according to

Jan 1, 1965

Ultrasonic Extinction for High Resolution Particle Size and Concentration Analysis

Sep 13, 2010

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y' phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS' showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By Alfred H. Hesse, Edwin T. Myskowski

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

By V. S. Tuman

In the first part of this paper, an estimate is made of the magnitude and extent of the thermal stresses which result from mud circulation. Our study is made for the period of relaxation, i.e., when the drilling operations are terminated and mud circulation is discontinued. In the second part, we have shown how the thermal stress can affect the wave propagation. An example is worked out for a Carbondale sandstone (Illinois basin). It is concluded that, in extreme cases when differential temperature is about 100°F, the travel time will be affected by about 2 microsec/ft. For more refined permeability studies, such corrections would be desirable. MAGNITUDE AND EXTENT OF THERMAL STRESSES RESULTING FROM MUD CIRCULATION When geological beds are penetrated by boreholes, it is observed that the formation temperatures increase with depth; however, the temperature profile varies considerably from place to place. During drilling operations, mud pumped from a pit at atmospheric temperature absorbs heat from the lower beds. As a result, the drilling fluid returning to the surface is at a higher temperature than the surrounding beds. The temperature gradient in a well depends on the rate of mud circulation and other factors; normally, this temperature gradient is smaller than the natural gradient in the formations. (See Fig. 1.) The temperature difference between the mud column and the surrounding beds gives rise to therma1 stresses (which are also important in the phenomenon of fracturing), and it is expected that they will affect the transit time of the sonic front in velocity logging.1 It is evident chat beds near the surface will undergo various cycles and will have a complicated dynamical and thermal-stress history. A limestone bed which is just penetrated will act as a source of heat, warming up the cold mud pumped down a few minutes earlier from the surface pit. The same limestone bed a week later will act as a sink, absorbing heat from the drilling mud which has already warmed up sufficiently to be at a higher temperature than the bed in question. No doubt a large section of the hole will undergo a heat treatment, which will make the calculation of the exact magnitude of the thermal stresses very difficult. In the solution of wellbore thermal equation, it is assumed that the rock around the wellbore is elastic and isotropic, and that the system is radially symmetrical. A complete dynamical solution of the thermal stresses set up at different horizons during the drilling operations would require a comprehensive history of the mud circulation, the surface temperature of the pit and the number of hours in which mud was not circulated. CONDUCTION OF HEAT AND THERMAL EQUATION OF STATE

By Edwin T. Myskowski, Alfred H. Hesse

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

By H. L. Luo

SYSTEMATIC investigations of the Fe-Ga system have been reported only very recently."' The maximum solid solubility of gallium in a-Fe is nearly 50 at. pet at 900°C. However, from Ref. 1, it was not evident that the a-Fe solid solution could be retained successfully beyond 17.38 at. pet Ga by solid-state quenching. The present investigation reports the retention of a-Fe solid solution at 50 at. pet Ga by quenching from the liquid. An ordered phase of CsC1-type B2) structure was observed between 34 - 50 at. pet Ga. Since it was considered very probable that the CsCl structure would occur at high temperatures, alloy filings were also quenched by the conventional quenching technique. In addition to the CsCl phase, a second ordered phase of BiF3-type (DO3) structure was found in the range 25 - 30 at. pet Ga. Alloys were prepared from elements of 99.99 pet purity or better, induction-melted in alumina crucibles under hydrogen. After reweighing, the alloy ingots were cast into wires under argon. From the weight losses and the reproducibility of the lattice parameters, compositions were estimated to be within ± 0.3 at. pet. The techniques of quenching from the liquid state were reported before.3-5 Prior to quenching, a small section of cast alloy wire (30 - 50 mg) was melted in an alumina insert under an argon flow. The quenched specimens were in the form of flakes, typically 1 sq mm in area. For solid-state quenching, alloy filings passing 200 mesh were sealed under a reduced helium atmosphere in a thin-bottom silica tube. After heating for -30 min at the desired temperature in a vertical furnace, the sealed tube was rapidly dropped into ice water so that the thin bottom of the tube broke on impact. The quenched alloy filings were always ferromagnetic and could be collected by a magnet. X-ray diffraction patterns were taken with iron-filtered cobalt radiation in a 114.6-mm-diam Debye-Scherrer camera. High-angle lines were always resolved and spacings were computed relative to ? (CoKa1) = 1.78890Å. Lattice parameters were obtained from extrapolation against the Nelson-Riley function. The variation of lattice parameter with composition is shown in Fig. 1, together with the data of Dasarathy and Hume-Rothery.1 Uncertainties in the present measurements are within the dimensions of the symbols or indicated by error bars. X-ray diffraction lines indicative of CsC1-type ordering could be clearly identified for alloys of 34 - 50 at. pet Ga quenched from the liquid and alloys of 35 - 41 at. pet Ga quenched from -975°C. Within experimental error, no difference in

Jan 1, 1968

By S. R. Zimmerley, John Gross

"The investigation discussed in this paper was undertaken to obtain fundamental data on crushing and grinding and has been confined, so far, to work on quartz.The results of crushing or grinding have hitherto been judged entirely by the amount of the various-sized particles produced, based. on sieve sizing for particles above 74 microns in size and on microscopic measurement or elutriation for particles below 74 microns - a method which could give only a general idea of what had been accomplished.There was a distinct need of a ""yardstick"" for the measurement of crushed material. It appeared that no advance in the fundamental investigation of crushing and grinding could be made without a reliable method of surface measurement and that such a measurement would have to be based on some property of the surface of the crushed material.A number of attempts based on various surface actions, such as adsorption and heat of wetting, were made to measure surface on quartz particles, but all gave unsatisfactory results. After some preliminary work it was decided that a dissolution method based on Wenzel's law-- ""the reaction velocity between solids and liquids is proportional to the area. of contact""4 -- would be the most feasible.Early use of the dissolution method had been made for surface measurements5, and lately Dr. Geoffrey Martin and his coworkers in England used the dissolution method to determine surface on quartz. They compared the amount of quartz dissolved from a sample in one hour by a hydrofluoric acid solution, with the amountdissolved from a measured quartz cuboid6,After investigating the solvent power of sodium carbonate, sodium hydroxide, and hydrofluoric acid for quartz, hydrofluoric acid was selected as the most suitable solvent, and a dissolution method was developed which gives very reliable results.During the dissolution of quartz in hydrofluoric acid, the reaction velocity changes for two reasons: there is a change in concentration of solution, and a change of surface of the solid. The amount of quartz dissolved in a definite period of time is therefore not a true measure of surface. If, however, the reaction velocity or rate of dissolution for various periods of time be plotted, a curve will be obtained which, if extrapolated to the zero time ordinate, will give the rate of dissolution before any change of surface or any change in the solvent has taken place, and which is a true index of surface. This rate of dissolution, expressed in percentage of the original sample at the zero time ordinate, is designated herein as the ""Initial Rate"" or as simply ""I. R."""

Jul 1, 1928

By J. Keough

During industrial electrowinning of copper, uneven growth can impact current efficiency, cause short-circuits in the cell and negatively impact the final quality of the metal product. Copper electrodeposits can be made smoother by incorporating a host of additives in the electrolyte but uneven copper growth may still occur due to variations in electrolyte composition throughout the cell-house. To quantify roughness, 3D images of the surface may be combined with scaling analysis to gain further insight into the deposit structure. Moreover, scaling analysis may offer a method to predict long-term deposit structure using short-term copper deposits. In this paper, the application of Atomic Force Microscopy (AFM) and scaling analysis are used to monitor copper growth and extract surface roughness characteristics. The cathode was a 304 stainless steel disc that was polished to a mirror finish. Copper was deposited onto this surface over a range of 10, 20 and 30 minutes from an acidic sulfate solution (40 g/L Cu) at 40oC from an electrolyte that contained or was free of guar. AFM images were acquired to obtain 3D topographical information on the samples and scaling analysis was performed to extract the root-mean-squared (rms) roughness, periodicity (grain size), aspect ratio of surface features and growth mechanism. INTRODUCTION During the process of copper electrowinning, the dissolved metal ions are reduced and thereby deposited onto a cathode substrate which is later recovered by stripping the metal from the cathode surface. Although this process is widely used in the industry, the conditions of the deposition procedure may cause the growth of the metal product to be uneven which can not only impact the current efficiency and final copper product quality but may also lead to plant interruptions through short-circuits if the anode and cathode make contact. To create more uniform copper deposits, a host of additives may be included in the electrolyte which may act as brighteners, leveling agents and inhibitors which may include guar gum, glue, thiourea or polysaccharides or polyacrylamides and their industrial use has changed over time (Moats, Luyima, & Cui, 2015). As such, the electrolyte composition is often complex and subtle variations in the solution matrix throughout the cell-house may impact the surface morphology of the final copper product. In an effort to quantify the roughness of copper samples, image analysis is often applied and may include Scanning Electron Microscopy (SEM) or Atomic Force Microscopy characterization. While both are appropriate, AFM offers 3-dimensional information which may be used to both qualitatively and quantitatively characterize the surface characteristics.

Jan 1, 2019

By Fritz F. Prugger

This paper considers some of the main aspects of underground mining in the flat, rich, but deep lying deposits of Saskatchewan. It briefly describes the pertinent geological features as they relate co mining and the practical de-stressing techniques used to allow productive extraction in the high stress environment present in many of the province's mines. Fining layouts, materials handling and the evolution of some of the world's largest mining equipment are examined.

Jan 1, 1980

By G. W. Healy, J. C. Schottmiller

Molten silicates were found to exist in the Cr-Si-0 system at temperatures above 1450°C. one atom of oxygen is readily removed from CrzOs in the presence of Si02 at 1700°C, forming a silicate melt. Steam-hydrogen ratio measurements made at this temperature indicate that the free energy of the reaction: Cr20s(c) + Hz = 2CrO (in Si02 -saturated melt) + H20 is approximately 5600 * 1500 cal. A deep-blue chromous silicate, probably Cr2Si04, forms from these melts at about 1400" to 1500°C, and is characterized by.its distinctive X-ray diffraction pattern and optical properties—distinct pleochroism and high refractive indices. THE question of the state of oxidation of chromium in slags has vexed metallurgists for many years The experiments of Koerber and Oelsenl suggested the probable presence of divalent chromium in silica-saturated slags equilibrated with high-chromium melts. Hilty and coworkers2 had also found chromium at lower valency, as Cr304, in inclusions formed from oxygen-saturated Fe-Cr melts with as little as 10 pct Cr. In both cases, disproportiona-tion of the lower oxide to CraO3 and chromium was found to occur to a greater or lesser extent, depending upon the rate of cooling from the high temperature. The work on Cr304 was sufficiently detailed for chipmans to derive its thermodynamic properties, but Oelsen's experiments in the silicate system were not extensive enough since most of his runs were made with slags containing large amounts of manganese oxide in addition to iron and chrome oxide and silica. The present study describes experiments carried out to map out an approximate liquidus diagram in the CrzOs, "CrO", SiOa portion of the Cr-Si-0 system, and to measure the partial free energy of solution of oxygen in the system. EXPERIMENTAL 1) Approximate Melting-Point Determinations. Preliminary trials showed that when an equimolar mixture of Cr20s and SiOa was treated with hydrogen in the temperature range 1500" to 1600°C, copious amounts of steam were evolved, and a low-melting liquid formed which could be quenched to a blue, crystalline, material having a distinctive X-ray diffraction pattern. It was found that the identical material could be produced by heating intimately mixed, finely divided Cra03, Cr, and SiOa, held in a tungsten crucible, under purified argon. Thus, it was possible to prepare mixtures containing any desired proportions of chromium, silicon, and oxygen, pel-letize them, heat to temperature in the furnace shown in Fig. 1, and observe, after cooling, whether the pellet remained unchanged or showed signs of incipient, partial, or complete melting. 2) Free Energy of Solution of Oxygen. This was studied by measurement of steam-hydrogen ratios for the reaction: H20 (gas) + O (dissolved in charge) + Ha (gas) The experimental method chosen was to prepare a

Jan 1, 1964

By R. S. Shoemaker, F. W. McQuiston

SOUTH AFRICAN MILLING PRACTICE All modern South African gold plants operate primarily on the principle of exposing the gold particles in the ore by fine grinding and then cyaniding the total pulp. Although there are minor variations and occasional depart- ures from established practices among the fifty gold mines in South Africa, the normal plant operations proceed as follows. After removal of waste rock by hand sorting (15Y0 on average) the ore is crushed in cone crushers to minus 1/2 inch and then ground to approximately 75% minus 200 mesh by milling with either rod, ball or pebble mills as primary units and pebble mills for the secondary grind. Classification in both circuits is almost invariably conducted with 20" cyclones of 30" or larger diameter. Gravity concentration in the milling circuit followed by barrel amalgamation of the concentrates is practiced in 70Y0 of the plants, particularly where the ore grade is high. A slightly better overall recovery is obtained than with direct cyanidation, but additional handling is involved. Johnson cylinder s , plane tables or belt concentrators, all lined with suitable types of molded rubber riffles, are used for this purpose. At all mines, cyanidation is the main process, usually conducted by continuous treatment in Pachuca tanks and pulp separation with rotary drum filters. Cyanide solutions contain about 0.0 1570 NaCN and require a protective alkalinity of 0.02070 CaO. Precipitation of the gold from cyanide solution is exclusively by zinc dust and lead nitrate using the Merrill-Crowe system in conjunction with Stellar pressure filters. The zinc precipitate is smelted, generally after a preliminary concentration by sulfuric acid, in electric furnaces, mostly submerged arc types, with a silica and borax flux, yield- ing a bullion of 8870 gold, 9% silver, and 370 base metals. The gold content of the ore varies between 0.20 and 1.0 oz Troy per short ton and extraction efficiency ranges from 9570 to 9870. In general, 4070 of the gold output is recovered by amalgamation and 6070 by cyanidation; but in some cases, it is entirely by cyanidation. Flotation has not been adopted for gold extraction as it has not proved as efficient as cyanidation. It is, however, often applied to ores containing higher than 1% sulfur for the recovery of pyrite for sulfuric acid production. On the eastern side of the Witwaters rand Basin, "run-of -mine milling” was introduced in 1960 and in three of the four mills in this area both sorting and crushing have been eliminated. The ore received from the shafts is conveyed to storage silos and then fed by Williamson automatic feed controllers to pebble mills ranging from 12 to 14 feet diameter, and 16 to 20 feet long. The pebble mills operate in closed circuit with 42 inch cyclones and the slime produced is thickened and cyanided in the conventional manner. No selective

Jan 1, 1975