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By E. E. Wark, I. W. Wark, J. Rogers. K. L. Sutherland

Soaps have hem used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xan-thates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present cminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies. † A broad, semiquantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. The Paraffin Chain Salts 'he basic requirements for a "collector " in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polar-nonpolar compounds is the paraffin chain salts: CH3(CH2)nX where .X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -Co2Na, -So3Na, -So4Na, — PO4Na2, or an aminonitrogen group, the

Jan 1, 1947

amounted to about 2000 metric tons. The total output is increasing from year to year. Marine salt is now produced in Haiti in quantity sufficient to supply nearly all the requirements of this Republic, so production tax is now collected. Central America Guatemala-The major production of salt in Guatemala is solar salt derived from sea water, but the Indian population prefers salt derived by boiling coastal marine earth. Salt is taxed by the Government. The industry has been beset by controversies in recent years, especially following the revolution of October 1944. The Government issued a decree in August 1940 designed to control production and price of salt. The creation of a salt consortium was provided for and marketing was to be governed by production quotas. It is understood that the Government pool was later dissolved and the industry is now under older laws whereby production and sales have no limits. South America Panama-Output of salt in Panama in a very recent year was 11,000 net tons of solar-evaporated sea salt. A Government bank is in charge of output and distribution of the product. Colombia-Rock-salt deposits are known in five places-Zipaquira, Nemocon, and Sesquile, in the Department of Cundinamarca, the Cumural y Upin near Restrepo, and San Miguel y Barital, near Medina in Meta Intendency. The latter deposit never has been worked on account of its inaccessibility. Saline springs are worked in four locations. The largest producer among marine salinas is Manare but it is now planned to make Bahia Honda the largest. Some evaporated salt is made in vacuum pans. The deposits at Zipaquira, Nemocon, and Sesquile are believed to occur in the domal type of deposit. All the salt resources are under Government control. Venezuela-The salt industry in Venezuela is under Government control and is taxed. Taxes in recent years, however, have been reduced for salt used in curing hides and salting meats, fish and fish products. Production has approximated 25,000 metric tons yearly but may now be considerably above that figure. The basin on the peninsula of Araya, State of Sucre, which at present is the only important source of salt, could produce at least 175,000 metric tons if more ground were provided-a larger supply than the entire country could consume. This unique landlocked basin of nearly 1000 acres lies 12 ft below sea level. Ecuador-Salt is a Government monopoly in Ecuador and is produced chiefly by solar evaporation close to the shore. The main producing center is on the Santa Elena peninsula, which supplies about 90 pct of the salt. Small fields are at Punta Arenas, Payana, and Chara-

Jan 1, 1949

By M. E. True, B. L. Stone

To cope with the problems encountered when drilling at greater depths and to reduce the amount of physical effort required on the part of drilling crews in making round trips, a new type of semiautomatic power-operated drilling machinery has been developed which permits round trips to be made without the drill pipe being touched by hand. This equipment consists of hy-draulically operated tongs which perform the stabbing, spinning, and tong-ing operations, and two power-operated racking units mounted in the derrick for carrying the pipe to and from the center of the hole and positioning it on the mat and in the rack. With this equipment all of the operations of the various units are controlled remotely by manipulation of hydraulic valve levers and electric switches. INTRODUCTION As horsepower rises to meet the demand for deeper drilling, it is necessary to increase the weight of surface drilling equipment. Also, the duration of repetitive operations in making round trips to change bits is greatly increased with depth. Harder formations encountered at greater depths reduce bit life rapidly, resulting in more frequent round trips and in some instances more time is consumed in changing bits than in drilling. Since the introduction of the first rotary employed to drill for oil in 18951, there has been relatively little change in the general procedure for making up, breaking out, stabbing, and racking drill pipe in making round trips to change bits. The conventional method of making round trips with the drill pipe requires that drilling crews lend strenuous physical assistance to manually operated tools. Although many new devices have been developed to improve efficiency, increase speed of making round trips, improve safety, and reduce the amount of physical effort required in handling drill pipe, it is considered a vital necessity to substitute automatic or semiautomatic power-operated machinery for many of our more or less manual operations if extremely deep drilling is to be carried out successfully on a production basis in the same manner as our shallower drilling of today. Field tests have been made of remotely controlled power-operated tongs, spinner, stabber, and racking equipment. The tongs, which include a built-in pipe spinner, are mounted on a column, are capable of gripping and supporting the weight of a 90-foot stand of drill pipe, and are provided with means for moving the pipe vertically as well as to and from the center of the hole. The racking equipment consists of two units, one at the level of the conventional monkey board and the other at the first girth on the ladder side of the derrick. Most of the physical effort of making round trips with drill pipe has been eliminated in that all of the operations of tonging, spinning, stabbing, and racking of pipe on the floor are controlled by an operator in a seated position by manipulation of hydraulic and electric valve levers and buttons. The driller is relieved of operating the cathead, leaving only the hoisting and slips to be controlled. Complete round trips are made without the drill pipe being touched by the drilling crews. Although the speed of pulling or running a single stand with the power-operated equipment is approximately the same as that with conventional equipment, it is possible to maintain this rate for long periods, whereas fatigue slows crews working conventionally during round trips, especially under adverse weather. After completing round trips with this equipment, drilling crews are not exhausted, consequently, are able to perform effectively their duties while drilling, which is essential for maximum over-all efficiency. Safety is substantially improved as the derrickman performs his duties from a platform enclosed by rails and the tong lines and spinning chain are eliminated from the derrick floor. The hazards encountered in racking drill pipe on the floor and in stabbing are also eliminated. Figure 1 shows a drawing of a derrick equipped with the power-operated drill'pipe handling equipment.

Jan 1, 1949

By M. Ahlers, Horace Pops

Slip features and formation of stress-induced mm-tensite have been studied in single crystals of fl phase Cu-Zn alloys in the composition range between 43 and 48 at. pct Zn. A phenomenological analysis is presented in which the glide planes and directions that me associated with the inhomogeneous shear in the martensite phase are predicted from the experimentally determined habit planes and macroscopic shear directions. It is shozun that the resolved shew component of the applied stress on the secondary shew system is a very important factor governing the formation of stress-induced martensite. A comparison is made between martensitic phases that form spontaneously upon cooling and those phases that arise from deformation. THE ß phase in Cu-Zn alloys is unstable and may transform spontaneously by a martensitic transformation1-3 during cooling. Thermoelastic and burst-type spontaneous martensitic phases have been observed3 in the composition range between 38 and 42 at. pct Zn. Martensite forms in alloys containing more than 42 at. pct Zn only by cold work below a temperature denoted as Md.4 Thus, alloys near the equiatomic composition can undergo a stress-induced transformation upon cold work at room temperature. Although data have been obtained concerning the effect of temperature5 and composition4 on the deformation of polycrystalline Cu-Zn alloys, it is rather surprising that few detailed studies6-8 on 6 brass have been conducted for single crystals where the stresses acting on crystallographic planes can be determined. A thorough understanding of transformation mechanisms requires knowledge of the role of stress and plastic strain. With this objective in mind we have made an investigation of the stress-induced rnartensite transformation in single crystals of 0 brass in the composition range between 43 and 48 at. pct Zn. Particular emphasis is given to the morphology and crystallographic features and a comparison is made between stress-induced and spontaneous martensite. I) EXPERIMENTAL PROCEDURE Master alloys having nominal zinc contents of 43, 45, and 48 at. pct were prepared from spectroscop-ically pure metals (>99.999 pct) in sealed quartz tubes under a partial pressure of helium. These alloys were cut into several pieces and converted into small rods by melting in quartz tubes. Subsequently, single crystals were grown from the rods by the Bridgman technique and homogenized for 3 hr at 820°C. Lattice parameter measurements were made from stress- relieved filings. Compositions, as determined from the reported variation of lattice parameter with atomic percent zinc,' indicated a zinc loss of less than approximately 0.25 at. pct. The single crystals were electroturned using a phosphoric acid electrolyte into tensile specimens each with a center section of 1 mm diam and 1 cm gage length. Cylindrical specimens approximately 3 mm in diam and 10 mm long and spark-machined rectangular blocks approximately 3 by 3 by 10 mm were prepared for compression studies. These blocks were stress-relieved and electropolished to eliminate any stresses introduced by spark machining. Crystal orientations were determined to an accuracy of ±2 deg primarily from back-reflection Laue photographs, and sometimes by the rotating single-crystal method. Figs. 1 to 3 show the location of the tension and compression axes within unit stereographic triangles. All specimens were deformed plastically at room temperature using an Instron machine, the crosshead speed being 0.02 or 0.05 cm per min. A hard steel hemisphere was placed at the upper end of the compression samples to achieve uniaxial loading. Trace normals of slip markings and habit planes of strain-induced martensite were determined to an accuracy of ±4 deg from the rectangular blocks by a two-surface analysis and from cylindrical specimens by measuring the angle between the tensile (or compression) axis and the tangent to the surface trace for different rotations about the deformation axis. Slip

Jan 1, 1969

By Strathmore R. B. Cooke, Paul B. Queneau

The kinetics of the dissolution of scheelite in basic solutions of carbonate and fluoride were investigated. Work was also done with solutions of alkali metal chloride, hydroxide, phosphate, and mixtures of phosphate and fluoride. The study was conducted at 90 psig and at temperatures ranging from 100" to 155"C, and both natural and synthetic scheelite single crystals were used. The interaction of scheelite with carbonate solutions generally followed a parabolic rate law, and resulted in the formation of calcite crystals on the attached surface. The transport of the CO3 through the calcite to the scheelite surface was probably rate -controlling between 115" and 135°C. Positive deviations from Parabolic behavior were observed at 100" and 155?C, presumably due to the calcite grain growth, and to the formation of a noncoherent calcite layer, respectively. The leaching of scheelite with alkaline fluoride solution produced a calcium fluoride reaction-product which covered the surface as a sheet-like layer. Below 110°C the dissolution rate was parabolic; at 115" and 135°C it was linear. In the linear region, the periphery of the calcium fluoride layer lifted from the sample. Only the lower layers, braced by the scheelite substratum, remained unbroken. This bound layer, approximately constant in thickness, limited the rate at which the fluoride could attack the scheelite. The phosphate and phosphate-fluoride leaches dissolved scheelite at a linear rate; solid reaction products were respectively hydroxyapatite and fluorapatite. Sodium hydroxide and chloride were not effective leachants, and did not produce observable solid reaction products. THE feasibility of pressure leaching of scheelite pulps with basic solutions containing either carbonate or fluoride ions, as indicated by the following equations, has been established by previous investigators:1-3 200°C CaWO4s + CO37q - CaCO3s+WO4aq [1] 200°C CaWO4s + 2Faq ^ CaF2s+WO4aq [2] It is to be noted that a commercial process employing reaction [I] is in use at Union Carbide's operation near Bishop, Calif. In the earlier work referred to, it was apparent that the precipitation of the solid reaction-product on the scheelite particles sharply reduced contact of the leachant with the scheelite. We have extended this work by studying the kinetics of dissolution employing single crystals of scheelite of known exposed surface area. In addition, the effectiveness of solutions of phosphate, of phosphate with fluoride, and of chloride and hydroxide as leachants for scheelite have been investigated. EXPERIMENTAL Apparatus. The low-pressure autoclave used in this wo (100 psig maximum) is essentially that of J. Halpern4 as modified by F. A. Forward.5 Constructed entirely of 316 stainless steel, its maximum capacity is 4000 ml. The temperature in the autoclave was regulated to *0.5?C by a Wheelco thermocouple controller. A 4-in. diam, three-bladed impeller, circulated solution upward against the sample, and a strobo-scope permitted holding the stirring rate to *15 rpm. A check valve and a "pop" type safety valve were installed, a sample holder was fixed to an externally adjustable rod, and a water-cooled condenser was placed in series with the sampling valve. The stainless steel sample holder, Fig. 1, held the epoxy-mounted sample (f) five mm above the impeller. Tightening the tapered sleeve (d) positioned the epoxy-resin specimen-mount by forcing it back against the spacer (c). The mount (e) was 1 in. diam. Sample Description and Preparation. Both synthetic and natural scheelite crystals were leached. The former were single crystals of 99.95 pct purity which were leached approximately perpendicular to the "c" axis; they were supplied by the Gallard-Schlesinger Chemical Manufacturing Corp. The natural crystals, supplied by Minerals Unlimited, were transparent, analyzed 99.8 pct CaWO4, and in ultraviolet illumination exhibited the characteristic blue glow of substantially molybdenum-free scheelite. To permit exposure of an essentially constant surface area of scheelite to the leachant, the samples were mounted in Scotchcast Brand Resin No. 250 (Minnesota Mining and Manufacturing Co.). The mount-

Jan 1, 1970

C. W. GENNET, JR.,* Chicago, 111. (written discussion?).-Since the Lehigh Valley accident, transverse fissures have become a source of constant anxiety to railroad officials, because such defects, only infrequently detected by the trackmen, may appear under a moving train entirely without warning. The number of actual accidents resulting from rails containing fissures is no doubt a small proportion of the total, but the serious losses that have been directly attributable to fissures, coupled with the continual possibility of repetition, creates an alarming situation which demands a full investigation of the cause of fissures; apart from other types of rail failures. Mr. Howard's position gives him a field for action and an opportunity for laboratory examination and research that are unsurpassed, and the results. of his investigations must be received with the utmost attention and respect. His admirable paper, summarizing his previously published studies and analyses of the transverse fissure problem, constitutes a convincing treatment of the subject chiefly from the standpoint of stress and strain to which rails are subjected. The intricacies of the problem are so great that seemingly any theory advanced for the cause of fissures may be attacked from some angle; and although Mr. Howard's deductions are logical in the direction followed, it is apparently necessary for considerable work to be done along other lines before his theories can be fully accepted. It is generally conceded that fissures, whether fundamentally clue to fatigue or something else, are of a progressive character, their ultimate size' being the result of growth from an originating nucleus or point of rupture. Abundant proof of this lies in the variable sizes of the fissures found, and there can be no doubt that their development or growth is the result of the strains to which rails are subjected in the track. Obviously, therefore, the most important factor in investigating the cause for fissures lies in determining the conditions that exist at the point or

Jan 4, 1918

By B. Ramaswami, Y. Nakada, U. F. Kocks

Compression tests were performed on single crystals of aluminum, silver, gold, and a Ag-10 pet Au alloy, with height-to-width ratios from 8:1 to 1:1. As this ratio decreased, so did the amount of easy glide until, for cubic specimens of all the pure materials, it was entirely absent. Heterogeneity of deformation is proposed to he a major contribution to the explanation of easy glide in slender specimens. For comparison, one single-crystal cube of zinc was tested and showed a behavior very similar to that in tension. Beyond easy glide, tension and compression curves are very similar. It is concluded that, in this range, neither grip effects nor orientation change influence the work-hardening characteristics to any significant extent. (121) and (100) crystals of all materials had similar stress-strain curves in tension and compression, except that the stress level of the flat portion of aluminum (109 crystals at high strains mas somewhat higher in compression. These results are at variance with previously proposed mechanisms of orientation dependence by both Hosford and Kocks. The compression tests themselves are described in detail and it is shown that they are essentially frictionless and produce single slip when the crystal is suitably oriented. DEFORMATION in uniaxial compression does not necessarily give the same result as deformation in uniaxial tension, essentially because the boundary conditions chosen are practically always different. 1) The shape and size of the specimens are usually different, and any genuine effect of size on work hardening should thus influence the result. 2) The grip constraints are usually different and can vary substantially for different kinds of tests. If the compression specimen is a thin plate and the friction on the platen is large, the grip contraints are more serious than in tension and lead, in the extreme, to uniaxial strain rather than uniaxial stress. If the specimen is roughly cubical and the friction is low, the specimen is less constrained than in tension inasmuch as displacements in the contact face are allowed. 3) The orientation change of single crystals is of opposite sign in tension and in compression; it is furthermore different in detail, because the relevant orientation in a squat specimen is the normal to the contact face, whereas that in a slender specimen is the generator of the side faces.' The considerable dependence of work hardening on the initial orientation in tension would suggest that the orientation change should also be very important. 4) Finally, localized deformation instabilities found in tension tests, such as necking and Lüders band propagation, are not possible in squat specimens. This is, for some investigations, a favorable consequence of the large grip influence. Even if one is not interested in any of the effects mentioned above, compression tests are often desirable just because the specimens needed are so much smaller and sturdier. For example, they have been very helpful in the investigation of latent hardening by means of alternate longitudinal and lateral compression of cubes,* and for testing

Jan 1, 1964

By Hallet R. Robbins

Korea, the ancient" Hermit Kingdom," is a peninsula jutting out from the coast of eastern Asia. By the natives it is called " Chosen," nfhich, translated, means " Land of the Morning Calm." It lies between the Yellow sea and the Sea of Japan. On the north it is separated from Manchuria and the Russian province of Primorsk by the Yalu and Tiumen rivers; on the south the Korcan straits interpose a rough voyage of 120 nliles to the nearest point in Japan. The entire country is situated between the parallels of 34O and 42O N. latitude. The surface of the country is made up of successive ranges of ul~glaciated mountains, separated by narrow, fertile, and more or less densely populated, valleys. Through all the obscure centuries of its history, Korea has succeeded in maintaining a monastic seclusion, over which, from time immeniorial until the late Chino-Japanese war in 1894, China exercised a shadowy sovereignty. Although Korea had been forced into slight foreign contact previously, her first forcign treaty was signed with Japan in 1876. Under the restraining guardianship of China, the Japanese treaty bore but infiignificant innovations for Korea; but when, in 1883, a treaty was made with the United States, the first of the western nations, a decade after the American gunboats, under Commodore Rodgers and Lieutenant Schley, forced their may up the Salee river, Korea awoke from her sleep of 4,000 years. The Eorean peninsula suddenly became the arena where the enterprises and individuals of many foreign nations met in fiercest rivalry. Out of this struggle grew two singularly successful American enterprises, both of which have played an important part in developing the natural resources of the country. The first, and best known of these, is the Oriental Consolidated Mining Co., which was organized by Lcigh Hunt

Jan 1, 1909

By Arthur B. Cummins

Mineral fillers are employed in United States industries to the extent of more than seven million tons annually, valued in excess of a hundred million dollars. This substantial usage involves a wide variety of mineral materials. To this may be added products manufactured from minerals, such as carbon black, portland cement, lime or chemically precipitated calcium carbonates, which would add substantially to the total. The purposes for which fillers are used differ considerably. Minerals used as fillers are mostly silicates, silicas, and carbonates as referred to hereinafter. The term "mineral filler" has various meanings in mineral technology and in the arts. Fillers are comparatively inert and their action is mainly physical. Materials that are employed primarily for chemical reactivity, or for pigment or abrasive functions ordinarily would not be considered to be fillers when used for these purposes. Nearly all filler usages are based on advantages which are gained by desired modification of composition properties or by improvements in processing. A simple definition for a filler is an inert material that is included in a composition for some useful purpose. This definition may be amplified or made more specific for each of the filler usages, the major ones of which are: paints, paper, plastics, rubber, bituminous compositions, pesticides and fertilizers. There are in addition a whole host of minor usages. Powdered minerals when employed as components in paints, varnishes and lacquers are considered as extender pigments or low refractive index pigments. In paper, the term loading material as well as filler is used; in pesticides, the terms diluents and carriers connote different functions. For bituminous compositions, rubber and plastics, the usage of the simple word "filler" is more usual, but the designation loading material is sometimes used. Minerals Used as Fillers Most of the industrial minerals, and many rock powders are employed to some extent for different filler uses. These usages vary from year to year depending on availabilities, costs, technologic trends and advancements. For the major applications, however, and for the more particular requirements at any given period, there are general trends which favor a more or less restricted group of filler products for each of the major consumer fields. This selection of materials is determined by the characteristics of the individual filler products, their effectiveness in fulfilling the primary function or functions for which they may be employed, and the cost after incorporation in the finished product. The mineral-bearing materials of major importance as fillers are: limestones, clays of several types, talc, pyrophyllite, mica, barite, diatomite, crystalline silicas, asbestos, slate and other rock dusts. Others of secondary importance include: gypsum, vermiculite, phosphate rock, perlite, and pulverized wastes, such as slag and fly ash. A considerable number of other minerals are used to lesser extent. Among these minor mineral materials are: feldspar, pumicite, wollastonite,18 tripoli, nepheline syenite,6 coal, altered volcanic rock and others.2 Indeed, most mineral materials, when reduced to fine particle size may have some potential usage as fillers, depending on their properties, availability and price. On the other hand, the more exacting filler requirements

Jan 1, 1960

By J. S. Aronofsky

The results of polentiometric model studies and numerical computations are described. The purpose of these studies was to determine the influence of the mobility ratio on flooding efficiencies during water encroachment in petroleum reservoirs, in systems of regular well geometry. The direct line drive well pattern having relative spacing distances of one and one-half to one was investigated for water to oil mobility ratios of 10. 1. and 0.1. The results of these studies indicate that the pattern Sweep efficiency i.; very dependent upon the mobility ratio. INTRODUCTION The almost universal occurrence of water in the immediate neighborhood of oil-hearing sands lends considerable emphasis to the desirability of having a rational analysis of water encroachment into petroleum reservoirs. This problem has 1)become increasingly important with the accelerated use of water injection for secondary recovery operations. The water encroachment problem has been studied from both the theoretical and experimental viewpoints by Muskat.' He has formulated, in a precise manner, differential equations to express flow in a water encroachment system, and rigorous analytical solutions have been developed for the linear, radial, and spherical cases.' However, it becomes exceedingly difficult to solve the encroachment problem rigorously for any general two-dimensional system in which the shape of the two-fluid interface is not immediately evident from the geometry of the system. The difficulty lies in the fart that a rigorous analytical solution requires that the shape of the two-fluid interface be known simultaneously with its instantaneous posititon and with the pressure distribution on both sides of the interface. Although this paper concerns the study of the two-fluid system of oil and water. the methods described in the paper are generally applicable to other systems of incompressible and immiscible fluids in which the displacing fluid sweep-the displaced fluid down to a residual value. In each region it is assumed there is only one mobile fluid and its mobility is constant throughout the region. The Same procedure. with minor alteration, is applicable for gas injection systems provided the assumption can be made that both the displaced and displacing gases can be described by steady state formulas. For the particular two-fluid problem considered in this paper, there is a relative permeability. K, and a viscosity. p. associated with the water zone, and a different permeability and viscosity associated with the oil zone. The K/p (mobility value associated with a particular volume element of the porous medium. at any instant of time. will depend upon whether the element is ahead of. or behind the advancing interface. It is assumed that all volume elements ahead of the interface are characterized by the K/p value for oil, while all the elements behind the interface are characterized by the K/p value for water. That is. the K/p value in the oil zone is constant throughout the oil zone. and the K/p value in the water zone is also constant but different from the value in the oil zone. The symbols are defined at the end of the paper. The well pattern chosen for initial study is the direct line drive; the swept-out area at breakthrough was determined by two different methods which are described in the section on theory. These are: 1. Potentiometric analyzer 2. Numerical computation The use of the potentiometric analyzer for studying water flooding problems is adequately described in the literature, particularly for cases where the mobility in the water zone is assumed equal to the mobility in the oil zone." ' 5

Jan 1, 1952

By H. H. Rachford, D. W. Peaceman

A system of partial differential equations describing miscible displacement of fluids in porous media is derived The system takes into account the influence of gravity, the spatial distribution of permeability, diffusion, and fluid viscosities and densities. A numerical procedure for approximating solutions to the differential systems has been tested for a horizontal two-dimensional geometry. In end-to-end displacements of oil with less-viscous solvents, the numerical solutions exhibited fingering qualitatively similar to that observed in laboratory models. Small random spatial variations in permeability about the mean value are sufficient to initiate fingering. Quantitative comparisons of computed results with laboratory data show good agreement. INTRODUCTION Miscible flooding of oil by solvent is receiving increasing consideration for field use.1-4 Unfortunately, such floods potentially present severe problems in loss of recovery through the by-passing of oil by expensive solvent. Consequently, their economic evaluation requires sound techniques for predicting recovery. The purposes of this work are to present a finite-difference method for calculating the multidimensional displacement of oil by solvent and to investigate the validity of the method by comparing results of calculations with data from displacements in laboratory models.5 The formulation of the method to simulate the model experiments treats a case of limited scope in the description of solvent flooding in the reservoir. The model experiments were carried out with fluids that were assumed to form an incompressible, ideal, two-component system with constant diffusivity. Establishing the validity of the method even in its present form provides a major step toward the goal of quantitatively evaluating individual solvent flooding projects. First, it demonstrates the fea- sibility of calculating the course of displacements which are dominated by an inherent macroscopic instability, i.e., viscous fingering. In addition, the method provides almost the only practical means of examining the effect of the size and extent of reservoir inhomogeneities on the development and propagation of the fingers, taking into account the important influences of diffusion and gravitational segregation. It might be inferred that such studies cannot yield results of practical value because in displacements dominated by macroscopic instability the pattern of finger development and the resulting performance should depend critically on small variations in the geometric distribution of reservoir inhomogeneities. The present method offers the capability inherent in computational techniques of predicting performance reproducibly with any arbitrary distribution of reservoir properties and, as such, provides a means of evaluating the sensitivity of behavior to uncertainties in reservoir definition and, thus, assessing the reliability of prediction of performance. THE PHYSICAL PROBLEM DATA USED FOR QUANTITATIVE TESTS OF CALCULATIONS In this work, a calculation for treating the miscible-displacement process is tested by comparing calculated results with experimental data. The experiments chosen for comparison have been described in detail,5 and the quantitative features are summarized in a later section. Briefly, oil was flooded by solvent of equal density from a thin rectangular channel in Lucite packed with uniform Ottawa sand. Under these conditions, two-dimensional geometry is considered adequate to represent the process. Inasmuch as the present work is concerned with testing of the method by comparison with specific two-dimensional data, the system of equations presented in the succeeding section will be oriented to defining the physical system specifically. THE DIFFERENTIAL EQUATIONS Suppose x, y to be a Cartesian co-ordinate system and define h(x, y) to be the height of a point above a horizontal reference plane. It will be assumed

By C. L. Thornburg

FLANKING the Valley of Mexico on the northeast is a mountain range known as the Sierra de Pachuca. This northwesterly-trending range is about 30 miles long and 5 miles wide, its summit attaining an elevation of more than 10,000 feet above sea level, or 2000 feet above the valley floor. Pachuca, a town of 50,000 inhabitants, lies nestled at the southwest base of the range, 60 miles northeast of Mexico City. Three miles to the east, just over the summit and on the northeasterly slope, is the mountain town of Real del Monte with a population of about 20,000. These are the two principal towns in a 40-sq mile area whose yield has brought the district to its high rank among the world's silver producers. Total production probably exceeds 1.25 billion ounces of silver and 4.5 million ounces of gold. Exploitation by the Spanish was under way by 1530. As the mines were deepened operations became handicapped by the inadequate method of handling water with horse whims and bull skins. To offset this disadvantage a two-mile drainage tunnel was started in 1749 and completed ten years later. John Taylor of London acquired the mines from the third Count of Regla in 1824 and formed the Compania de Real del Monte y Pachuca. Two years later Cornish pumps were brought from England. A Mexican company purchased the British interest in 1848 and within a few years resumed an old project of driving a second, lower three-mile drainage tunnel, completing it in 1857. After Americzn interests acquired control of the property in 1906 operations expanded to an unprecedented scale, despite periods of political strife, unstable prices, labor problems, and a growing burden of taxation. An idea of the scale of operations may be gained from records of the last two decades prior to 1947, the last year for which production information is at hand, during which time production ranged from 1.4 million to 1.1 million tons per year, and the combined development and exploration, exclusive of diamond drilling, amounted to about 18 miles annually. Pachuca differs from Zacatecas and some other Mexican silver vein districts that flourished and de- clined in earlier centuries in that a substantial part of its total production was made after 1900. While the district's accelerated activity in this century was largely due to the successful application of the cyanide process to the treatment of the ores, improved pumping methods, and new mechanical equipment, it was at the same time stimulated by the opening up of important new orebodies as a result of active and extensive exploration of the vein system. Some of these orebodies were found on veins which terminate upward far below the surface, and though these particular veins do not crop out, they show relationship with a type of alteration which may be their surface expression. The district has been studied by many able geologists, and a large store of information has been accumulated, much of which is recorded in published as well as private papers. Wall Rocks Extrusive Rocks: The Sierra de Pachuca is a thick accumulation of Tertiary eruptive rocks consisting mainly of flows, breccias, and tuffs. Numerous recognizable volcanic vents within the range itself manifest that the range was built up by material ejected from these vents. The maximum thickness of the volcanic pile is not known, but from deep exploration and from relationship with Mesozoic sediments to the north and east it is inferred that the average thickness in the main part of the district may be at least 6000 ft. The extrusive rocks comprise four general types, which in ascending order of age are: andesite, rhyolite, dacite, and basalt. The veins are confined largely to the andesite, the dominant rock of the region. Characteristically this rock is augite andesite, but it includes comparatively acidic as well as basic layers, the acidic strata being

Jan 1, 1953

By John P. Hager, Igor A. Wilkomirsky

The thermodynamic properties of the Pb-Ag system have been determined between 775° and 950°C by the cell: Electrotransport measurements on silica-saturated PbO-SiO2 melts established that the conduction was entirely ionic and that lead is present only in the divalent state. The activities of lead and silver exhibit Positive deviations from ideal behavior. In dilute solutions the activities of lead and silver follow Henry's law. The values obtained for yhb and yig at 1200°K are 1.49 and 1.69, respectively. Determination of a portion of the liquidus curve agrees well with the established phase diagram. provides an accurate means for the thermodynamic study of liquid alloy systems. However, Wagner and wernerl have shown that cells of type I are limited to alloy systems for which the reaction at the alloy-electrolyte interface will be extremely small. The traditional electrolyte for cells of type I has been a low melting point mixture of group IA chlorides, to which a small amount of the compound ACIZa has been added. However, the choice of a chloride electrolyte may not always be practical, in that the Gibbs free energies of formation of the compounds ACIZ, and BCIZb may not be sufficiently different to minimize Reaction [I]. On the other hand, the Gibbs free energies of formation of the oxides of metals A and B may be sufficiently different to minimize Reaction [I]. In this case, the use of molten oxide electrolyte would be clearly advantageous. In the present study, the thermodynamic properties of the Pb-Ag system have been investigated using the cell: Previous galvanic cell studies on the Pb-Ag system2'= are not reliable due to the displacement reaction between the alloys and the chloride electrolyte. Wagner and ~erner,' using Laitinen and Liu's' value at 450°C for the standard electrode potential of Reaction 111, have estimated the percent error in the activity of lead bPb) when using a chloride electrolyte. At 1000°C the error for xpb = 0.10 is 12 pct. Taking the Gibbs free energies of formation for PbClz and Ag cI,' and the equations of Wagner and Werner,' the error in apb at 1000°C and Xpb =0.10 was calculated to be 140 pct. However, using the Gibbs free energies of formation for Pb O' and an estimated value for Ag 20, the error in apb when using a molten oxide electrolyte at 1000°C was estimated to be less than 1 pct for The virtual reaction of cell I1 for the passage of n Faradays of positive electricity from left to right in the cell is: where 5 is the Faraday equivalent (23,063 cal per v equivalent), E is the electromotive force of the cell in volts, and n is the number of Faradays of electricity required for the transfer of 1 g-atom of lead through the cell. The value of n should be equal to 2 since lead is generally divalent in oxide melts. However, the presence of either tetravalent lead ions or electronic conductivity through the molten oxide electrolyte will result in a value of n greater than 2. Bockris, Kitchener, and Davies' have determined the amount of ionic conductance in a liquid PbO-SiO2 mixture (xPbO= 0.50) at 920°C by measurement of the volumes of CO and C& evolved at a carbon anode during electrolysis. From their data a value of 2.13 * 0.16 was calculated for n. Although their measurements indicate the possible presence of multivalent lead ions and/or electronic conductivity, their measurements were not at silica saturation and no definite conclusions can be drawn. However, as a result of the electrotransport measurements described in the next section the ;due of n can be taken as equal to 2.

Jan 1, 1969

Jan 1, 1894

By D. C. Hilty, W. Crafts

The solubility of oxygen in iron containing aluminum has been determined at 1550°, 1600°, and 1650°C and found to be much higher than predicted from theoretical considerations, possibly due to equilibria with an iron-aluminum spinel phase rather than pure AI,O.. The presence of manganese greatly increased the deoxidizing power of aluminum. DEOXIDATION and inclusion formation in steel have proved to be elusive phenomena that are difficult to control in spite of much effort to understand and evaluate the reactions. Study of the problem indicated that more accurate data on the solubility of oxygen in iron containing deoxidizers were essential to further progress, and an empirical determination of oxygen solubilities has been initiated at the Union Carbide and Carbon Research Laboratories, Inc. The investigation has included the effects of aluminum, silicon, manganese, and combinations of these elements at 1550°, 1600°, and 1650°C. The equipment and experimental procedure as well as the results of a study of the effects of aluminum are described below. In general, it was found that the solubility of oxygen in iron containing aluminum is much higher than predicted, possibly because of the formation of complex nonmetallic phases, and that manganese greatly increases the deoxidizing power of aluminum. The generally accepted deoxidation curves for 1600°C are summarized in fig. 1, from "Basic Open Hearth Steelmaking"'. These curves are assumed to represent the solubility of oxygen in the presence of deoxidizers and should indicate the limits of mis-cibility gaps in the phase diagrams of the systems that control the formation and character of non-metallic inclusions as described by Benedicks and Lofquist'. They were derived mainly by application of the methods of thermodynamics to the available experimental observations, and by calculations based on the thermal constants of the pure substances when experimental data were lacking. Among the more notable researches contributing to the development of knowledge of oxygen solubilities are those of Korber and Oelsen8, 4, C. H. Herty, Jr. and associates5,6, Krings and Schackmann7, Went-rup and Hieber8 Schenck and Briiggeman9, Vacher and Hamilton'" and Chipman and co-authors 1,11,12,13 Practically, the deoxidation curves are of limited value in predicting oxygen content and rationalizing deoxidation practices. The reasons for this inadequacy appear to be error from inaccurate data, oversimplifying assumptions, interacting effects of combined deoxidizers, and possibly unknown extra-equilibrium and side reactions. Although inclusion formation is a very complex reaction it must be re-

Jan 1, 1951

By Lars Thomassen, Ernest Kirkendall, Clair Upthegrove

THE amount of research done in the last few years on the subject of diffusion in solid metals is significant of the importance of this problem. To review the literature dealing with diffusion is unnecessary here. Desch1 in 1912 reviewed the work that had been done on diffusion in solids and gave a bibliography of the literature published before that time. Mehl's paper in 19362 is an excellent review of diffusion in metals and contains a large bibliography. Of importance also for its review and bibliography is an article by A. I. Krynitsky.3 While considerable material has appeared in the literature on diffusion in brass, the amount of information is not great compared to that pertaining to some of the other alloys. Most of the information published is of a qualitative nature; that which is quantitative varies considerably. Thus the quantitative determination of the rates of diffusion of copper and zinc in alpha brass by a new method appeared worth while. In the present investigation the rate of diffusion of zinc in approximately the same composition alpha brass has been determined at three temperatures. PROCEDURE The method used consisted of plating copper on a beta brass, heating it to allow diffusion to take place, and measuring the concentration of copper by determining the lattice constant of the alloy. This method is unique in that it uses a beta brass of such a composition that at the temperature at which diffusion takes place the beta brass is saturated with copper. Thus, while the beta brass supplies the zinc, no diffusion takes

Jan 1, 1938

By G. H. Anderson

During an investigation of the copper-rich portion of the copper-silicon-iron system as part of an extensive research program on P.M.G. alloys, which was begun in 1937 in the research laboratory of the Phelps Dodge Corporation, it became apparent that the binary copper-silicon system below 7 per cent Si needed revision, therefore an investigation was undertaken. Both X-ray methods and microscopic technique were employed. Despite the many investigations that have the clarification of this system as their object, no two successive reports on the system have agreed in placement of the alpha-phase solubility limit, and uncertainty about the secondary phase first to appear has been voiced several times.3,4,5 It was therefore not surprising, when T. Isawa's6 and M. Okamoto's7 works were reported at the time we were finishing up our experimental work, to find essential disagreement between their results and ours. But when C. 5. Smith's latest work on the copper-silicon systema was published just as we were finishing our laboratory report, it was indeed gratifying to find that the latter's diagram and ours checked in all essential features, except the temperature of the peritectoid line above 830" C. Many attempts were made to retain the beta phase during the present investigation, but none was successful. Isawa,6 however, reports that he has been able to obtain X-ray photograms of the beta phase. The structure, he states, is body-centcrcd cubic with a lattiee constant of 2.848 ,&. at 7.2 per cent Si. Okamoto7 and Smith8 both use the designation Kappa for the hexagonal phase, and to avoid confusion this designation will he adhered to in the present paper. Preparation of Samples The alloys were melted in vacuum in a high-frequency furnace. from copper cathodes containing 99.98 per cent Cu, and specially refined silicon supplied by The Electro Metallurgical Co. This silicon is stated

Jan 1, 1940

By J. C. Scully, G. Sanderson

The electrolytic formation of y hydride in thin foils of Ti-5Al-Z.5Sn alloy and four Ti-A1 binary alloys has been studied by electron microscopy and electron diffraction. Two orientation relationships have been found: THE adsorption of hydrogen by titanium alloys from aqueous solutions has been widely reported. This can occur, for example, in both alkaline' and acidic2 pickling baths, in chemical polishing374 and electro-polishing Solutions,3,4 during cathodic polarization5" and under certain corrosion conditions,7,8 Etching reagents may also produce visible precipitates, sometimes after an aging period.9 During an investigation into the stress corrosion susceptibility of a titanium alloys by thin foil electron microscopy many observations have been made of hydride precipitation which has been deliberately promoted by techniques that are described below. The characteristics of hydride precipitation are reported and the observed crystallographic orientation relationships are discussed with reference to distortion in the titanium lattice created by the presence of the hydride. EXPERIMENTAL TECHNIQUE One grade of commercial titanium and five alloys were examined. Their composition and hardness values are shown in Table I. All the materials were in the form of thin sheet, 0.05 to 0.065 cm thick, which had been annealed after cold rolling. Foils suitable for transmission electron microscopy were made in two ways: a) by chemical polishing; and b) by elec-tropolishing. The solution used for chemical polishing was a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. During this polishing specimens were manually moved up and down in the solution. The reaction was veFy rapid, specimens thinning to foil thickness (2000A) in 5 min. Since chemical polishing solutions tend not to cause hydride contamination if they are kept cool3 no attempt was made to prevent the solution from becoming hot during the thinning operation. Electropolishing was performed at -30° C with a mixture3 composed of 295 cu cm methyl alcohol, 175 cu cm n-butyl alcohol, and 30 cu cm perchloric acid with an applied voltage of 40 v after chemically thinning specimens to approximately 0.017 cm thickness in a cool solution of 44 pct HF, 40 vol H2O2, and water in the volumetric ratio 1:6:3. EXPERIMENTAL RESULTS 1) Ti-5A1-2.5Sn Alloy. The Ti-5A1-2.5Sn alloy was severely contaminated by hydrogen during the chemical polishing. Foils obtained in this way contained large amounts of the y hydride phase. A typical micrograph is shown in Fig. l. The laths were identified as the hydride phase by selected-area diffraction of a large number of foils examined in a tilting stage that could be turned through 40 deg. Using the lattice spac-ings of the alloy obtained by X-ray diffraction as a standard the a value of the hydride was determined fromo the electron diffraction patterns to be 4.38 to 4.40A. The accuracy of this figure is only about ±2 pct. Further evidence of the identification was obtained by vacuum annealing chemically polished foils of the alloy at 500°C. This resulted in the dissociation of the hydride with the production of dislocations and possibly vacancy loops as shown in Fig. 2. The hydride

Jan 1, 1968

By C. W. Hill

IN a previous article preliminary experiments were described, indicating the possibilities of a quantitative spectroscopic method for the determination of small amounts of lead in copper, which would be accurate and rapid, and could be carried out in the refining plant by one not skilled in chemical analysis. The present paper deals with the development of the method in the factory, giving the details of apparatus and its standardization, and presenting a comparison of the accuracy of the method with that of the standard electrolytic determination. (For variations and other applications of the method, the reader is referred to the first article.) FIG. 1.-STEPS IN THE ELIMINATION OF LEAD. (The lead line, at point 105.8 in the violet portion of the spectrum, is seen between the two copper Lines,-102.29 and -106.29, lying close to the latter. The crowded faint lines are due to the carbon are.) 1. OUTLINE OF METHOD A carefully weighed sample (0.4 gm.) of the copper to be tested is placed in a cavity in a graphite positive electrode. An arc capable of

Jan 10, 1918

By Anthony Tuke

Members of the Society of Mining Engineers may well regard it as rather unusual that a paper on this subject is being presented by someone whose first taste of mining came at the age of 60 or so - someone who last heard of cathodes and anodes in 1938. On the other hand, the title does refer to the financing of a mine and at least I can claim to have spent all my business life since the war until 1981 in the world of banking, though this inevitably means that I have been used to looking at these and other problems through what you might regard as the wrong end of the telescope. The lending of money, and more particularly the provision of finance for commerce and industry, is the central job of a banker and I have been involved in this in various ways over many years, but regrettably only very marginally in the world of mining. As you will see from what follows, the rather specialised form of finance which RTZ required was, to my regret, not provided by the British banking community since the great majority of the finance came from American banks and, to a lesser extent, from German banks. I am most indebted to Mr. Roy Wright for a great deal of the nuts and bolts in this paper. He was one of the three central figures in the growth and expansion of RTZ during the 1950's and 1960's and was right at the centre of the negotiations with bankers, with governments and with many others. The going, as you will see, was far from easy. The essential basis for the financing of each of the RTZ group's mining projects was a firm long-term sales contract for sufficient of the output of the particular mine to produce the cash flow necessary to service the loans. Wherever possible, loans were raised in the same currency as the sales contracts were made. Each sales contract was designed to give the customer the product he wanted with a long-term assurance of supply and at the same time to give the bankers the protection they required. Thus the marketing concept and the financing concept for a particular mine formed one overall plan, and talks with the customers and the bankers were conducted in parallel until a satisfactory marketing/financial package was agreed in principle. Preliminary talks were begun soon after the discovery of a potentially viable orebody. As confidence about a discovery increased, customers were persuaded to enter into contingent sales contracts before the very detailed and costly business of the economic and technical feasibility study of the mine was launched; such a study might cost 10% or more of the estimated total capital cost. At the same time provisional understandings were reached with the bankers. The contingent sales contracts usually gave a period of grace of eighteen months to two years, during which time the decision whether or not to continue with the mine had to be made. This decision rested mainly on the result of the feasibility study and also on coming to a firm agreement with the bankers. If all went well and the mine went ahead, then the contingent sales contracts became firm, but they fell away if the decision was negative. The Company was fortunate that during the whole period when its major mines were being developed, world trade was increasing rapidly and Japan was becoming a dominant industrial power. The Japanese supported many of the mines, including Hamersley Iron Ore, Lornex Copper, Bougainville Copper to name a few, with the basic long-term sales contracts that enabled their development. The Germans supported Palabora and to a lesser extent Bougainville. The mines were financed as individual projects generally with a loan/equity ratio of about 65/35, without legal recourse to RTZ for the loans. RTZ was, however, responsible for providing any capital overruns required to bring the mines into commercial operations. Nevertheless, the RTZ management regarded itself as morally responsible to the lenders because, Palabora aside, the sales contracts had either a fixed selling price (like Hamersley), an indexed price (like the Elliot Lake Uranium Mines and Mary Kathleen), or a floor price (as in Lornex, Bougainville and Rossing). Thus the Company believed that any financial failure would have been due to poor management or technical

Jan 1, 1985