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By R. J. Blackwell, J. R. Rayne, J. R. Henderson, W. M. Terry, D. C. Lindley

This paper presents the results of a laboratory investigation of the efficiency of water-solvent mixtures in recovery of oil. These mixtures may have the high displacement efficiencies characteristic of solvent floods and the high sweep efficiencies characteristic of water floods. Thus, the water-solvent process may increase the number of reservoirs in which a miscible-type displacement can be used profitably. The experiments on the use of water-solvent mixtures for recovery of oil were conducted to find the general applicability of the process. These studies demonstrated that, in flowing through sands, water and solvent segregated into a solvent layer on the top and a water layer on the bottom rather than flowing through the sands as a uniform mixture. Calculations based on the simultaneous flow of the water and solvent in layers were used to predict the effective mobility of the mixtures and the optimum operation of the process in steeply dipping, homogeneous reservoirs. As most reservoirs are not suited for the operation of the process under ideal conditions, experimental studies were conducted with sand-packed models scaled to represent more realistic reservoirs. These studies included the effects on recovery of oil of rate of injection, viscosity of oil, variations of permeablity within a formation and variations in water-solvent ratio. For the range of con-ditions studied, higher recoveries of oil were obtained with water-solvent mixtures than with water or practical volumes of solvent alone. INTRODUCTION A group of intriguing—because of their great possibilities—new oil recovery methods at the disposal of the petroleum engineer are the miscible displacement processes. These processes (high-pressure gas drive, en-riched-gas drive and LPG bank driven by methane) displace all of the oil from the portions of the reservoir swept by the injection fluid. The key question confronting the engineer applying one of these techniques to a particular reservoir is, "What fraction of the reservoir can be swept by injection of a practical volume of solvent?"." Intensive laboratory studies have been made during the past several years in seeking answers to the question of the sweep efficiencies which can be expected in solvent floods.' - These studies provided the answer that low-viscosity, low-density solvents channel and by-pass oil in sands with no dip. In horizontal sands, solvent flooding becomes less efficient as the viscosity of the oil increases, the recovery of oil at solvent breakthrough decreases and larger volumes of solvent are required to achieve a given recovery. More efficient displacement of oil by solvent is observed under certain conditions in sands with dip.".' If the permeability and dip of the sand are sufficiently high, gravity segregation of low-density solvent injected updip can prevent channeling. At rates of depletion below a critical rate,"." no channeling occurs. Unfortunately, in many reservoirs, the critical rate is so low that production of oil at rates below this rate is not economically attractive. And at rates over four times the critical rate, channeling is almost as severe in sands with dip as in horizontal sands. These findings pointed out that, for solvent floods to be generally applicable in recovering oil from all types of reservoirs, new methods of improving their sweep efficiencies are needed. Simultaneous injection of water with the miscible fluid was suggested by Caudle and Dyes7 as a method for improving sweep efficiencies. They theorize that water flowing with the solvent would decrease the effective mobility of the solvent and cause it to contact more oil sand. If, indeed, the water and solvent flowed as a uniform mixture, the process should have the advantages of the high displacement efficiencies characteristic of miscible floods and the high sweep efficiencies of water floods. Thus, the method (at least in theory) would greatly increase the number of reservoirs in which miscible-type displacements would be feasible. A research program was conducted to probe the technical feasibility of the water-solvent process. It

SAN FRANCISCO SECTION W. H. SHOCKLEY, Chairman, PRANK H. PROBERT, Vice-Chairman, T. A. RICHARD, Sec.-Treas., 420 Market St., San Francisco, Cal. C. C. BRAYTON, J. F. NEWSOM. The San Francisco Section met on September 11 to discuss the problem of Labor in its Relation to the Mining Engineer. Mr. W. H. Shockley was in the chair. T. A. Rickard opened the discussion under four heads: The recognition of the union, the rustling-card, the sliding scale of wages, and the' contract system. He expressed his belief that collective bargaining cannot be ignored, and insisted that the mining company represented a collective bargaining of its shareholders with the men. employed in its mine. He held that the contract system was often used unfairly, but that used fairly it was the best check on labor tyranny. The rustling-card he held to be right in principle, in so far as it gave the employer the choice of employees, but he believed that it was often used in an irritating way to black-list refractory laborers. The sliding scale of wages was easy to establish in prosperous times, but it would inevitably lead to trouble when conditions went against the miner. His conclusion was that the quarrels of labor and capital were due mainly to a lack of the sense of fair play and of social justice. Albert Burch agreed with most of the foregoing, and insisted that 90 per cent. of the men were inclined to be just, but that the 10 per cent: made all the trouble. He stated that he had introduced the rustling-card in the Coeur d'Alene in 1899, as a means for getting rid of agitators. E. L. Foucar considered that labor was irresponsible. He described his experience in Peru, where the authorities promptly stopped a strike of Italian miners by threatening prompt punishment for any display of violence. Morton Webber also gave a bit of his own experience, to show that the chief trouble is that the men do not think for themselves, and are therefore easily led by fomenters of trouble. F. H. Probert described his experiences in Germany and. also in Arizona, and insisted that too often the men were not given a fair hearing. E. T. Blake argued that a manager must get the workmen's point of view, in order to control them effectively. He believed that young men who started life doing manual labor were in a better position to understand their fellow workers. George J. Young suggested that the mine owners should encourage the good men to lead the unions, and not leave the direction of the unions to the noisy element.

Jan 12, 1917

By John Chipman, Daniel Dutilloy

The equilibrium of gaseolis H2O-H2 mixtures with liquid iron-phosphorus alloys in the range 0 to 3 pct P is used to establish the increuse of the activity coefficient of oxygen, in the presence of phosphorus. Two different sampling techniques are used. THE importance of oxygen as a refining agent in steelmaking operations makes it desirable to improve our understanding of its behavior. Phosphorus which is always present in the ores has adverse effects on steel properties and its removal is necessary. The present study was undertaken to evaluate the interaction of oxygen and phosphorus in molten iron. Bookey, Richardson, and welch1 have studied the phosphorus-oxygen equilibria in liquid iron in the presence of lime. They used a mixture of hydrogen and water vapor to control the oxygen potential and worked with crucibles made of tetracalcium phosphate and lime. At low phosphorus concentration, i.e., at high oxygen, they observed a marked deviation in their results. They tentatively ascribed this to a large negative effect of oxygen on the activity of phosphorus. This was then included by chipman2 in his review of interactions in liquid iron. Pearson and Turkdogan 3 have later reported an interaction parameter They equilibrated a mixture of hydrogen and water vapor with an iron-phosphorus alloy contained in an alumina crucible and sampled the melt by suction in a silica tube. The solubility of oxygen in iron-phosphorus alloys has been studied by Levenets and Samarin.4 They reported an interaction parameter

Jan 1, 1961

By J. Chipman, J. C. Fulton

Reduction of Si from slag to carbon-saturated iron is a very slow reaction. The rate is nearly independent of stirring but is accelerated markedly by increased temperature. In a slag containing 45 pct SiO2, 38 pct CaO, 17 pct Al2O3, the energy of activation is approximately 130 kcal. AT temperatures of 1450" to 1600°C occurring in the hearth of the iron blast furnace, chemical reactions are normally expected to proceed with great rapidity. Many of the reactions of iron making are indeed quite rapid and attain a condition corresponding roughly to a state of equilibrium before metal and slag are tapped from the furnace. The one conspicuous exception is the reaction by which carbon in the coke or metal reacts with silica in the slag to deliver silicon to the metal. From the practical viewpoint the slowness of this reaction is indeed fortunate, for if it were fast enough to reach equilibrium during the time of contact, it would be difficult to produce pig iron of the desired low silicon content. The one other reaction which under certain circumstances can also be very slow is the transfer of sulfur from blast-furnace metal to slag. In their laboratory exeriments on this reaction, Hatch and Chipman found that at least 5 hr were required for the attainment of equilibrium in a small crucible and that the reaction was not accelerated by increasing the rate of stirring. Subsequently it was shown2 that the presence of a reducible oxide MnO greatly inhibited sulfur removal, and finally that SiO2 itself3 under some conditions has sufficient oxidizing Dower to interfere with sulfur transfer. The kinetics of sulfur removal are now rather well understood,4 and it has been shown3,5 that when the silicon content of the metal is high enough to prevent reduction of SiO,, the desulfurizing process is rapid. Thus the observations of slow removal of sulfur are associated with the coincident slow reduction of SiO2, a process which transfers both silicon and oxygen to the metal phase. It is, of course, the oxygen which interferes with sulfur removal. An explanation of the slowness of the silica reduction reaction has not been obtained. The sulfur transfer process has been shown by the authors5 to be at least partially transport-controlled in the absence of interference by silica. Under the experimental conditions. 99 pct of the total transfer at 1600" was accomplished within an hour. Under similar conditions the reduction of silica may not proceed half-way to equilibrium6 in 8 hr. It is scarcely imaginable that silica reduction could be transport-controlled when the slag contains 44 pct SiO2 and the metal about 1.4 pct C. The experiments reported here show definitely that it is controlled by a slow step or steps in the chemical reaction. One might expect to find such a slow step in the breaking of SiO bonds or in the slow removal of oxygen by carbon at the slag-metal or metal-crucible interface or by bubble formation. EXPERIMENTAL PROCEDURE The experimental procedure used in this investigation was similar to that used in the study of the kinetics of desulfurization.5 A sketch of the graphite crucible and stirrer used in the current work is shown in Fig. 1. The quantity of metal and slag used was adjusted so that the slag-metal interface was located between the top and bottom blades on the stirrer; the top of the slag layer was above the top blade. The stirrer shaft was hollow down to the metal level and served as thermocouple well or optical pyrometer target. Stirring speeds of 0 to 500 rpm were used. A carbon monoxide atmosphere was maintained in the furnace by flushing the gas over the slag surface, except in run No. 220 when it was bubbled

Jan 1, 1960

By E. Miller, N. Chou, K. Komarek

The solid solubilities of the compounds PbS, PbSe, and PbTe have been determined by equilibrating single crystals with two phase alloys. The solubilities were determined by measuring the Hall coefficient of the equilibrated samples. The observed maximum deviations from stoichiometry on the lead rich and the chalcogen-rich side of the phase fields were: at. pct excess Pb at pct excess S at 850°C; PbSe--4 x 10'" at. pct excess Pb at at. pct excess at 800°C; and PbTe-2.8 x 10 4 at. pct excess Pb at 780°C, 10"1 at. pct excess Te at 720°C. The previously developed theory of retrograde solubility has been expanded to include intrinsic disorder in the compounds, and the experimental results are in agreement with the theory. THE solid solubility limits of intermetallic semiconducting compounds are of considerable interest, since many of these compounds have potential use as thermoelements in thermoelectric devices, as infrared detectors, or in semiconductor devices. The solidus curves of a significant number of these compounds have been reported to be retrograde with the maximum solid solubility occurring between the eu-tectic and the maximum melting temperatures. In a previous paper,' equations were derived which permit calculation of the maximum solid solubility of an AB compound exhibiting retrograde solubility. Derivation of these equations was based on the assumption that the compound is a nondegenerate semiconductor at the temperature under consideration, that the defects were unassociated, and that the vibrational contribution to the entropy of the compound could be evaluated by the Einstein approximation. It was shown that at the temperature of the maximum solid solubility The entropy term ASS is composed of the entropy of formation of the solid stoichiometric compound (AS$)*, and the entropy due to deviations from stoichiometric composition which is the sum of a con-figurational term (aS*), a vibrational term (AS,), and an electronic term (AS,). In the previous paper the positional entropy was evaluated considering the con- N. CHOU, Member AIME, formerly Graduate Student, New York University, N. Y., is with IBM, Yorktown Heights, N. Y. K. L. KOMAREK, Member AIME, formerly with New York University, is Professor, Department of Inorganic Chemistry, University of Vienna, Vienna, Austria. E. MI LLER, Member AIME, formerly with New York University, is Associate Professor of Mechanical Engineering, California State College at Long Beach, Calif. The paper is based on a thesis submitted by N. CHOU to the Graduate Division, School of Engineering and Science, New York University, in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Materials Science. tributions from defects arising from deviations from stoichiometric composition. The derivation is generalized in the appendix to include intrinsic disorder. The electronic entropy term is also recalculated in the appendix. Of the various semiconducting compounds, the solidus curves of Pbs,' and ~b~e,~ have been most extensively studied. The solidus of PbSe has also been determined, but the temperature of maximum solubility has not been accurately established.5129 The present investigation was undertaken to compare the experimental solid solubility data for these systems with the values predicted theoretically. Since the temperature and composition of the maximum solubility of PbSe has not been accurately determined, experimental emphasis was placed on determining the solidus curves for PbSe in the region of maximum solubility, although experiments were also performed on PbS and PbTe at several temperatures. X-ray diffraction studies were also made on carefully prepared powder samples of PbSe to determine the variation of lattice parameter with composition. EXPERIMENTAL PROCEDURE The procedure of Brebrick and Allgaier was employed for determining the solidus data. Monocrystal-

Jan 1, 1970

By G. L. Oldright, F. W. Schroeder

Very great changes were made in the dimensions of the smelting hearths of the furnaces in the period from about 1800 to 1906, the length increasing from about 11 to 116 ft., and the width from 8 to 19 ft. During this time the tonnage smelted increased from about 9 to 250 tons per 24 hr., and the tons of charge smelted per ton of coal increased from 0.77 to 4.3. Dr. Mathewson3 noted no great difference in the "fuel ratio" (i. e., the amount of charge smelted per ton of coal) as the furnace at Anaconda was increased in length by stages from 85 to 116 ft. (The percentage of copper in the slag, however, was lowered from 0.42 to 0.36 per cent. The other components of the slag were not given.) Lump coal fired on grates was the fuel used during this period. The practice in operating the furnaces over such a length of time naturally varied considerably, and there were differences in composition and nature of the charge, yet it may he considered that the improvements made were due largely to increases in the size of the furnace used. Doubtless some credit should be given to improvements in operating technique, like changes in the methods of firing the lump coal. However, the greater part of the advance was probably due to factors influencing the

Jan 1, 1928

By P. W. Bennett, E. M. Elkin

A new technique for the recovery of palladium and platinum and sludge from go12 electrolyte eliminates many of the drawbacks of the zinc-dust cementation process. In the electrolytic refining of gold by the Wohwill method, the electrolyte contains about 100 gpl gold as AuCl, and 100 gpl free hydrochloric acid. Any palladium and platinum contained in impure gold dissolve and accumulate in the electrolyte. When their concentration approaches that of gold, it becomes desirable to discard the electrolyte and to recover the gold and the palladium and platinum. As practiced at Canadian Copper Refiners until recently, discarded electrolyte was treated with sulfur dioxide to precipitate the gold. 2AuCl3 + 6H2O + 3SO2 —2Au + 6HC1 + 3H2SO4 The gold precipitate was filtered off, washed with water, and melted with scrap anodes. The wash water was added to the gold-free filtrate and treated with zinc dust to cement the palladium and platinum. PdCl2 + Zn — Pd + ZnCl2 PtCl4 + 2Zn—Pt + 2ZnCl2 The precipitate was separated and sold as Pd-Pt concentrate, and the barren filtrate and wash water were discarded. The receipts of palladium and platinum at this company were too small to warrant their refining. The process suffered from a number of disadvantages. Handling the gold-free solution was disagreeable, as it was laden with sulfur dioxide even after blowing with air overnight. Subsequent treatment with zinc dust was also troublesome. A large excess of zinc dust was required. Spray, acid mist, and vigorous evolution of hydrogen accompanied the reaction. The Pd-Pt precipitate was grossly contaminated with occluded unreacted zinc and with yellow granules of sulfur, thought to be formed by the reduction of sulfur dioxide and its derivatives. Repeated boiling of the precipitate with hydrochloric acid and washing with water decreased somewhat, but did not eliminate, the zinc. After drying overnight, the precipitate hardened to a clinkerlike mass that was difficult to grind. Grinding, handling, and packing created heavy dusting. Even weighing in an analytical balance generated dust, indicating that the powder was easily charged with static electricity. The total palladium and platinum content of the powder varied from 56 to 72 pct, with an average of 65 pct. The powder dissolved in aqua regia with difficulty, leaving a small amount of insoluble residue. However, the main drawback of the process was the strongly hygroscopic Pd-Pt product. The powder showed a marked though erratic increase in weight and a corresponding decrease in assay on exposure to air, even during the course of laboratory analysis. Such changes were the source of disagreement between Canadian Copper Refiners and the buyers of concentrate. The cause of the change in weight is believed to be hydrogen, liberated by the action of zinc dust on hydrochloric acid. Some of this hydrogen was adsorbed so strongly by the precipitate that it could not be driven off during the drying. On exposure to air it oxidized catalytically, forming water. Experiments soon showed that the entire process of treatment of discarded electrolyte then in use would have to be changed. A small quantity of apparatus was moved into the gold room, and experimentation was held to a minimum compatible with the development of a new process. PALLADIUM AND PLATINUM PRECIPITATION It was thought that zinc could be replaced with a reagent other than a hydrogen-evolving metal. Semiquantitative experiments showed that platinum and palladium could be precipitated completely from the gold-free solutions with such well-known reagents as sodium formate, formic acid, formaldehyde, and paraformaldehyde. Sodium formate was the preferred reagent, since the other three are volatile and somewhat toxic. The gold-free solutions used were those saturated with sulfur dioxide, partly freed of sulfur dioxide by aerating overnight, completely freed by boiling, as well as strongly and weakly acidic, neutral, and alkaline solutions. The reactions are complex and can be represented by these over-all equations: PdC1, + HCOONa — Pd + NaCl + HC1 + Co2 PtCl4 + 2HCOONa — Pt + 2NaCl + 2HC1 + 2CCX, Strongly acidic solutions required as much as five times the theoretical amount of sodium formate as did solutions neutralized to pH 4.5. Increasing the pH decreased the consumption of

Jan 1, 1965

By Albert J. Phillips

As EARLY AS 1824, Haidinger1 described crystals of native copper that were, according to Dana,2 "probably twinned parallel to the octahedral plane and normal to this axis." In 1837, Rose3 very clearly demonstrated that native copper crystals were commonly twinned on the octahedral plane. Lasaulx,4 in 1882, described polysynthetic octahedral twins and stated that enclosed twinning lamellae were observed. Even on crystals formed artificially by electrolysis, twinning was observed as early as 1886, by Brown.5 Many other descriptions of twinning in native copper and in gold and silver are to be found in the literature, and in every case with which we are acquainted the twinning is conformable to the spinel law; i. e., the octahedral plane is both twinning and composition plane. Metallurgists have long been familiar with the straight-sided bars or bands that commonly occur within the irregularly outlined grains of metallic crystalline aggregates. They are certainly found in nearly all metals of the face-centered cubic type after cold working and annealing. If a specimen showing these bands is rotated, keeping the angle of incidence of the illuminating beam constant, they usually exchange color contrast periodically with their respective matrix crystals. Also slip lines, when produced in these specimens, nearly always show a change in direction upon passing through the bands, giving rise to the "stairway" effect often illustrated in metallurgical textbooks. Apparently the only quantitative observations on bands of this sort were made by Osmond and Cartaud6 on austenitic steel. They selected,

Jan 1, 1928

By Kenneth Seaver

Discussion of the paper of KENNETH SEAVER presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 105, September, 1915, pp. 1913 .to 1927. J. W. RICHARDS, South Bethlehem, Pa.-This paper concerns a very large industry, and an important detail in that industry. Within sight of where I live in Bethlehem, Pa., are coke works in which $2,500,000 was lost by the use of improper bricks in the coke ovens. This was the fundamental reason of the failure of the plant. The old ovens have all been torn out and replaced by new ovens built of proper bricks. This may emphasize the commercial importance of this subject. When speaking about coke-oven brick, the first thing that comes to my mind is how important it would he if it were possible to. get a brick of better heat conductivity. The heat for coking coal has to go through the thickness of the brick. The silica brick used has low heat conductivity as compared with some other refractories; magnesite brick probably has four times its heat conductivity. The coke oven needs bricks of high heat conductivity. Any process which would increase the heat conductivity of silica brick would undoubtedly shorten the coking process.

Jan 12, 1915

By J. P. Sheeha, W. F. Craig, M. Baeyertz

The loss in toughness caused by phosphorus within commercial ranges was studied in AISI-SAE 1340 steel and in molybdenum modifications of this grade. The replacement of part of the manganese by molybdenum in amounts which maintain the hardenability of the standard 1340 grade was shown to counteract to a marked degree the detrimental effects of phosphorus. THIS paper deals with the effect of phosphorus on the toughness of 1340 steel and with the effect on toughness of replacing part of the manganese by molybdenum while retaining the same hardenability as that of 1340. In previous work1 a progressive decrease in toughness was observed when the phosphorus content of 5140 was raised from 0.020 to 0.036 pct; that is, from a moderate phosphorus level to one higher but yet within the AISI-SAE specification for this grade. The structural condition of the steel was tempered martensite. Toughness was evaluated by the transition temperature determined by V-notch Charpy tests. Replacement of a part of the chromium in 5140 by molybdenum provided a factor of safety against loss of toughness caused by phosphorus, especially where the steel was cooled slowly after tempering. Scope of the Study: In view of the improved tolerance for phosphorus obtained by replacing a part of the chromium in 5140 with molybdenum, it seemed desirable to investigate the possibility of obtaining similar improvement in 1340 by replacing part of the manganese with molybdenum. Heats were made at different phosphorus levels, in a series that began with 1340 and ended with steels containing 0.32 to 0.35 pct Mo with 0.82 and 0.90 pct Mn. The analyses of the heats are given in table I. In order to facilitate later discussion, the 1340 heats have been placed together in the order of increasing phosphorus content, and the molybdenum modifications have been grouped according to phosphorus

Jan 1, 1951

By Norman Brown, J. V. Rinnovatore

It was found that a shear stress applied during the recovery had no effect on the amount of recovery if the stress was less than the instantaneous yield point irrespective of the direction of the stress. Large ajplied stresses during recovery had a marked effect, which depended on the direction of stressing. Single strain reversals at -72°C not only produced the Bausch-inger effect but also increased the flow stress. The increase inflow stress was attributed to vacancies, which have appreciable mobility at -72 °C. THEORIES I-' of recovery suggest that the internal stress field of the dislocations plays an essential role. Most investigations of recovery use time and temperature as the independent variables; however, here stress has been introduced as a variable in two ways: 1) by varying the internal stress field according to the amount of strain prior to recovery and 2) by applying an external stress during recovery. Tannen- baum and Kauzrnann studied the effect of applying a stress during recovery by measuring the change in creep rate after recovery; they found that stresses as high as 95 pct of the creep stress had no effect on recovery. Earlier, Wood and scrutton6 showed that an applied stress during creep increased the rate of poly-gonization. The experiment by Wood involved poly-crystalline aluminum whereas Tannenbaum and Kauzmann used a single crystal of zinc. In this investigation, zinc single crystals were used and deformed in a manner to prevent polygonization. Thus, the main difference between this investigation and that of Tannenbaum and Kauzmann is the use of the stress-strain curve instead of creep rate as the index of recovery. In addition, the applied stress during recovery varied

Jan 1, 1961

By W. G. Lidman, H. J. Hamjian

' I HE fabrication of many materials from powders involves a sintering process. A mass of powder will sinter because of the excess free energy over the same mass in the densified state caused by the higher total surface area of the powder. An understanding of the kinetics and mechanism of sintering should assist in improving the properties of such materials. The present investigation conducted at the NACA Lewis laboratory deals with the sintering of chromium carbide. Dry sintering (sintering at a temperature below the melting point) was divided into two stages by Shaler:' the first stage, during which the particles preserve much of their original shape and the voids are interconnected, and the second stage, during which densification occurs and the pores are isolated. The mechanism of forming interfaces between particles, or welding together of particles, has been investigated by Kuczynski2 and may be described by any one or a combination of the following mechanisms: viscous flow, evaporation and condensation, volume diffusion, or surface diffusion. The mechanism by which pores are closed or eliminated (densification) during sintering, is of interest. Grain growth observed during sintering may be attributed to the variation in the surface energies of individual grains, causing some grains to grow at the expense of others. Grain boundary migration occurs presumably by a diffusion process, therefore the rate of grain growth would be expected to increase exponentially with increasing time and temperature. Thus, for practical sintering times of less than 1 hr, a certain minimum temperature may exist at which major structural and property changes will occur. Densification and kinetics of grain growth during sintering under pressure of chromium carbide were investigated to provide additional information which will aid in describing more accurately the sintering process and the mechanisms involved. This material was selected for this study because of the current interest in high strength, oxidation resistant refractory materials, such as carbides, which are sintered to produce solid, dense materials from powders. Sintering under pressure is a process where the heat and pressure are applied to the compact simultaneously, specimens for this work were prepared by sintering under pressure at different temperatures and for various time periods. Experimental Procedure Preparation of Specimens: Chemical analysis of the commercial chromium carbide used in this investigation was as follows: Cr 86.19 pct, C 12.14 pct, and Fe 0.2 pct. X-ray diffraction powder patterns gave characteristic diffraction lines of Cr3C2 crystal structure. Powder particle size was determined microscopically and the average initial particle size was 6 microns with 85 pct between 2 and 10 microns. Specimens sintered under pressure were formed in graphite dies3 heated by induction. Sintering temperatures were measured with an optical pyrometer by sighting into a 3/8-in. hole drilled 1 in. deep at the midsection of the graphite die. A load of approximately 1 ton per sq in. was applied to the powder. The die assembly was heated in 20 min to the highest temperature (2500°F') at which no increase in grain size could be observed, and less than 2.5 min were required to heat from this temperature to the maximum temperature (3000°F). Sintering temperatures and times for the specimens of this investigation are indicated in Table I. Analysis of Specimens: Specimens polished with diamond abrasives were etched to reveal the grain boundaries with a 1:1 mixture of 20 pct potassium hydroxide and 20 pct potassium ferricyanide heated to 160°F. Representative areas of each sample were photographed at 1000 diameters. The largest diameters of all well-defined grains were measured, but only the measurements of 15 of the largest grains were averaged in order to determine an index of grain size on the assumption that they were among the first to begin growth. Densities were determined from differential weighing of the samples in air and water. The reported density values are considered correct within ±0.01 g per milliliter. Results and Discussion Metal compacts have exhibited grain growth when sintered at temperatures about two-thirds of the absolute temperature of their melting point.' Grain growth also occurs during the sintering of chromium carbide and is illustrated by the micrographs shown in Fig. 1. These micrographs were prepared from specimens sintered for 90 min at temperatures ranging from 1371°C (2500°F) to 1648°C (3000°F). Average grain size and density measurements of specimens investigated are presented in Table I. The relationship between grain size and sintering tem-

Jan 1, 1954

By Kenyon Burch

ONE of the advantages presented by electric drive in many classes of work is the ease with which the electric motor can be controlled automatically. In a large number of cases certain features of the control are automatic-for example, the rate of acceleration may be limited automatically or the equipment may be stopped automatically at the limit of travel-but the equipment is started and ordinarily is stopped by hand. . In other cases the motion of the machinery is utilized to start, control the: speed, and stop the motor automatically, independently of any operator. A considerable proportion of the large mine hoists now in use have certain automatic features, particularly protective devices against over-winding, and, in some classes of electric hoists, devices for preventing excessive acceleration or retardation. The large automatic hoists discussed in this paper, however, are completely automatic, i.e., capable of snaking their trips without the presence of an operator at the control levers. According to circumstances, various advantages may be obtained by automatic control, chief of which are decreased power consumption', increased precision and safety of operation, and decreased, cost of attendance. The first step in the analysis of a prospective automatic mine hoist is to determine whether automatic operation is feasible at all. If men are to be hoisted, or levels changed, the attention of an operator is required for these purposes; but tinder some conditions it may be entirely practicable and advantageous to build the equipment so that, while provision is made for hoisting mien or changing levels, ore can be hoisted automatically from, any one level. If, however, an operator's attention is required every few minutes for changing levels, handling men or drills, or other work requiring hand control, it is obvious that automatic operation between times will not be of any, practical benefit.

Jan 3, 1916

By Kevin B. Doyle

The export markets are of great importance to western Canadian sulfur producers, taking 70% of total products sold. For these marketers, Canadians have always supplied solid sulfur, first in a crushed, bulk form, and for the past several years in a slate form. Both form have proved inadequate for safety and environmental reasons, and new forms and processes have been developed by interested suppliers. The Canadian industry has evaluated these processes and ha made a determination of a desired Product specfication that will greatly enhance the acceptability of future Products from safety, environmental, and customer points of view. The new processed methods and resulting product characteristics are reviewed.

Jan 1, 1980

By Marcel R. Daly

In a preceding paper1 the writer has pointed out some apparent relationship between the distribution, on the surface of the globe,, of the known hydrocarbon deposits and the disposition of the principal zones of deformation of the earth's body (geosynclines). He wishes to present some further remarks on this subject. Petroleum deposits, or their derivatives or descendants, are found through the whole range of sedimentary strata, from the pre-Cambrian to the Quaternary. For instance, the prc-Beltian (Shuswap) series of the Canadian Cordillera are interbedded with limestones which are sometimes rich in carbonaceous matter (Sicamous limcstone); and the Beltian system of the same region contains layers of argillitcs and dolomitic limestones which are equally high in carbon content.2 This carbon may be interpreted as the last remnant of hydrocarbons previously contained in the rocks. On the other hand, the actual formation of hydrocarbons under conditions that would eventually permit their deposition in modern sediments is conceded by some geologists.3 Between these two extreme limits, bitumens are found indifferently in all sedimentaries. Thcy constitute a continuous series, some kind of a large family, whose individual members may be entitled to a community of origin and probably represent the different stages of evolution of the primitive, parent matter. The kinship between petroleum and such substances as asphalt, ozocerite, manjak, grahamite, albertite, etc., is well known; and E. H. Cunning-gam-Craig has recently shown how intimately shale fields and oil fields are connectcd.4 For this reason, no distinction is made in the present

Jan 1, 1918

By Charles N. Becker

The practice of drying phosphate in Florida is as old as the industry, which began a little more than half a century ago. The methods, however, have changed considerably. At first, the natural process of exposure to the sun and air was used, later supplemented by wood fires beneath open-air stationary dry kilns and drying towers of various designs. It was not until the early nineties that rotary driers came into use, and at first they were of very small design and fired with wood. As the industry grew and tonnage increased, so likewise grew the number and size of rotary driers, until today the largest installations are 6 ft. up to 7 ft. 6 in. in diameter, and 55 to 60 ft. long, fired with crude oil. The reasons for drying phosphate rock are: (1) to eliminate freight on water in the shipment and (2) to facilitate the good grinding qualities required by the buyers in their acidulation. Phosphate pebbles vary materially in natural characteristics and each property has a direct bearing on the processing. In making comparisons of cost and operating conditions, the following are usually taken into consideration: 1. The hard dense pebbles, which contain very little interior moisture and 6 to 8 per cent total moisture, usually produced from the low-grade deposits. 2. The lighter, porous pebbles, which contain 4 to 5 per cent interior moisture and a total moisture ranging from 9 to 15 per cent. 3. The product of recovery operations using oily reagents, containing from 15 to 25 per cent moisture. 4. The size of the pebbles Usually the plus 5-mesh material is considered as "coarse rock"; the minus 5-mesh plus 24-mesh is "fine rock," and the minute particles below 24 mesh are called "concentrate." 5. The amount of moisture allowed in the dried product. The practice is generally to dry down to 1.5 to 2 per cent moisture. There is, however, an actual range in guarantee of from 1 per cent maximum to 3 per cent maximum.

Jan 1, 1938

By Charles N. Becker

The practice of drying phosphate in Florida is as old as the industry, which began a little more than half a century ago. The methods, however, have changed considerably. At first, the natural process of exposure to the sun and air was used, later supplemented by wood fires beneath open-air stationary dry kilns and drying towers of various designs. It was not until the early nineties that rotary driers came into use, and at first they were of very small design and fired with wood. As the industry grew and tonnage increased, so likewise grew the number and size of rotary driers, until today the largest installations are 6 ft. up to 7 ft. 6 in. in diameter, and 55 to 60 ft. long, fired with crude oil. The reasons for drying phosphate rock are: (1) to eliminate freight on water in the shipment and (2) to facilitate the good grinding qualities required by the buyers in their acidulation. Phosphate pebbles vary materially in natural characteristics and each property has a direct bearing on the processing. In making comparisons of cost and operating conditions, the following are usually taken into consideration: 1. The hard dense pebbles, which contain very little interior moisture and 6 to 8 per cent total moisture, usually produced from the low-grade deposits. 2. The lighter, porous pebbles, which contain 4 to 5 per cent interior moisture and a total moisture ranging from 9 to 15 per cent. 3. The product of recovery operations using oily reagents, containing from 15 to 25 per cent moisture. 4. The size of the pebbles Usually the plus 5-mesh material is considered as "coarse rock"; the minus 5-mesh plus 24-mesh is "fine rock," and the minute particles below 24 mesh are called "concentrate." 5. The amount of moisture allowed in the dried product. The practice is generally to dry down to 1.5 to 2 per cent moisture. There is, however, an actual range in guarantee of from 1 per cent maximum to 3 per cent maximum.

Jan 1, 1938

By A. Rosen, P. Wynblatt, J. E. Dorn

The temperature, strain rate, and structure dependence of the flow stress in a poly crystalline Fe-2 pct Mn alloy was investigated between 77" and 370°K. It was possible to identify the low-temperature data from 77° to 160°K with Dorn and Rajnak's theory of the Peierls mechanism of plastic deformation. Above 160°K one or more thermally activated mechanisms must he operative; however, these were not identified in this investigation. The mechanistic basis for the rapid decrease in the flow stress of bcc metals with an increase in temperature over the low-temperature range is yet being debated. Various dislocation mechanisms have been suggested in the past but the agreement between the various proposed theories and the experimental results have not been definitive. In the present paper, the authors will demonstrate that the plastic behavior of polycrystalline iron containing 2 wt pct Mn plus interstitials agrees excellently with predictions based on the Peierls mechanism from 77" to 160°K whereas from 160" to about 370°K other as yet unidentified thermally activated mechanisms take over. Undoubtedly, the overlap of these mechanisms with the Peierls mechanism contributed to the difficulties of rationalizing the low-temperature behavior of iron and its alloys. I) EXPERIMENTAL TECHNIQUES AND RESULTS Although extensive data are now available on the effect of temperature and strain rate on the flow stress of various bcc metals and alloys, it was, nevertheless, deemed necessary for the objectives of the present study to obtain highly accurate data of the type most pertinent for checking the theories on a series of well-documented work-hardened states. Iron containing 2 wt pct Mn was used in this investigation in order to obtain a lower ductile to brittle transition temperature than that for iron.' The additional elements present were 0.004 pct C, 0.05 pct 0, 0.004 pct S, 0.003 pct P, 0.006 pct N, and 0.001 pct Si. The as-received 3/8 by 3/4 in. bars were cold-rolled to 0.100-in. thickness, recrystallized under argon for 30 min at 1073"~, further cold-rolled to 0.063-in. thickness, and finally recrystallized under argon for 30 min at 1000°K. This treatment gave a stable reproducible equiaxed grain structure having an average grain diameter of about 90 p. Prior to the final recrystallization treatment, the sheet was machined into tensile specimens 1/4 in. wide having a 1.625-in.-long gage section. All specimens were tested in controlled-temperature baths on an Instron Testing Machine. For convenience in the theoretical analyses the data will be given in terms of the shear stress for flow, 7, the shear strain rate, f, and the shear strain, y. A series of three standard strain-hardened states were obtained by prestraining specimens at 300°K and at a shear strain rate of 7.68 x lo-' per sec to three stress levels of 6.89 X l08, 10.3 X lo8, and 14.5 x 10' dynes per sq cm, respectively. Immediately following this prestrain the temperature bath was changed and each specimen was pulled in tension at either f = 7.68 X lo-' or f = 3.06 X 10"3 per sec. In terms of the accuracy that was achieved, the values obtained did not deviate more than *0.1 X 10' dynes per sq cm and * 1°K from the reported values of stress and temperature and not more than *5 pct in the reported values of the strain rate. The tensile stresses were converted to shear stresses using a factor of 1/2. The shear stress for the initiation of flow at the test temperature was determined by taking a y = 6.16 x 10'3 offset. from the modulus line at which point good accuracy could be achieved in determining y and the associated flow stress 7, with only a negligible increase in the pre-

Jan 1, 1965

By B. A. Eaton, K. E. Brown, C. R. Knowles, D. E. Andrews, I. H. Silberberg

This paper presents the resitlts of an investigation of two-phase, gm-liquid flow in horizontal pipelines. Experimental data were taken in three field-size, horizontal pipelines, two of which were constructed for this purpose. The data were obtained using water, distillate and crude oil separately as the liquid phase, and natural gas as the second phase. Experimental pressure-length traverse, liquid holdup and flow-pattern data were collected for each set of flow rates. These data were used to develop three correlations that are presented herein. The liquid-holdup values correlated with various flow parameters without regard to the existing flow pattern. The same was true for the energy-loss factors. A new flow-pattern map is presented that appears to be quite reliable, but not required for the pressure-loss calculations. The liquid-holdup correlation and the energy-loss factor correlation are used in conjunction with a two-phase flow power balance, developed during this study, to predict the pressure losses that occur during gas-liquid flow in horizontal pipelines. A recommended calculational procedure is given, as well as a statistical analysis of the results. This procedure lends itself to computer application, since several small pressure decrements are needed to calculate a pressure-length traverse. The correlations are shown graphically, but may be curve fitted with existing curve-fitring computer programs. INTRODUCTION Due to the frequent occurrence of gas-liquid flow in pipelines and the desire to accurately calculate the pressure losses that occur in these lines, two-phase flow is of considerable interest to the petroleum, chemical and nuclear industries. In the petroleum industry, gas-liquid mixtures have been transported over relatively long distances in a common line due to the advent of centralized gathering and separation systems. Long two-phase flowlines are usually accompanied by large pressure drops which influence the design of the system. Gas-lift installations are designed on the basis of known tubing pressures at the wellheads. The horizontal flowline connecting the wellhead and the separator system must be correctly sized in order to minimize the horizontal flowline pressure losses and the wellhead tubing pressure. Practically all oilwell production design involves horizontal two-phase flow in pipeknes. All of the flow processes of oil and gas production must be studied simultaneously to insure good well design. Since the beginning of offshore oilfield development, long horizontal flowlines have been constructed. Because pressure losses greatly influence the performance of producing wells, a method is desired that can be used to predict such pressure losses and select optimum flowline size. Several types of gas-liquid flow exist, and many of these are discussed by Gouse The study of pressure gradients, fluid distributions and flow patterns that occur in horizontaI multiphase flow is made difficult by the great number of variables involved. The various flow regimes give rise to changing velocities of the fluid particles in all directions. These instabilities of the interface between the gas and liquid prohibit the determination of actual vector velocities of fluid particles in each phase. Also, it is practically impossible to arrive at correct sets of boundary conditions. Therefore, most investigators have concluded that a solution to the problem by the classical fluid dynamics approach, whereby the Navier-Stokes equationsM are formulated and solved, is far too complex. Other methods must be utilized to develop general correlations that will predict the behavior of gas-liquid horizontal flow systems. Multiphase flow studies have sought to develop a technique with which the pressure drop can be calculated. Pressure losses in two-phase, gas-liquid flow are quite different from those encountered in single-phase flow; in most cases an interface exists and the gas slips past the liquid. The interface may be smooth or have varying degrees of roughness, depending on the flow pattern. Therefore, a transfer of energy from the gaseous phase to the liquid phase may take place while energy is lost from the system through the wetting phase at the pipe wall. Such an energy transfer may be either in the form of heat exchange or of acceleration. Since each phase must flow through a smaller area than if it flowed alone, amazingly high pressure losses occur when compared to single-phase flow. Most investigators of horizontal two-phase flow phenomena have chosen to separate their experimental data into several groups of observed flow patterns or regimes.

By C. K. Stoddard, R. G. Knickerbocker, E. T. Leidigh, R. R. Lloyd, K. L. Mattingly

DURING July 1941, a study was initiated at the Boulder City Experiment Station of the Bureau of Mines on proposed methods for the production of magnesium metal. The major emphasis was placed upon development of a process that required minimum reliance upon the sale or utilization of by-products to meet economic competition from processes already in operation. It was felt that only through the development of such a process could the nation's vast resources of dolomite and low-grade magnesite that are contiguous to large blocks of firm power be properly utilized. During the course of exploratory tests on electrolytic and electrothermic processes, it was noted that fused magnesium chloride would dissolve appreciable quantities of magnesium oxide in the presence of small amounts of boric oxide. The use of such a solution in an electrolytic cell employing a graphite anode and a steel cathode caused the deposition of magnesium at the cathode and the evolution of carbon oxides at the anode with minimal amounts of chlorine The original results were sufficiently encouraging to justify further investigation on an enlarged scale, since the process seemed to present advantages over other proposed processes 1.2 for the direct use of magnesium oxide in a fused chloride electrolyte. When work on a larger scale was initiated it was found that the addition of boric oxide to the electrolyte resulted in dispersion of metal and constantly decreasing current efficiency. However, by this time solubility studies had shown that magnesium oxide was sufficiently soluble in magnesium chloride melts containing no boric oxide to effect the same anode reactions, and development work was continued. Over two years of development work have been carried out, and considerable work remains to be done. It is desired to emphasize the fact that many of the difficulties met require a long period of continuous operation before they become serious enough to affect operation of the cell. ACKNOWLEDGMENTS This paper is one of many reporting on various aspects of the Bureau of Mines' program initiated in August 1939 by passage of the Strategic Minerals Act the scope of which was greatly expanded by subsequent legislation. Some of these papers are published as war minerals reports. others as bulletins, technical papers, reports of investigations

Jan 1, 1945