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By Lyman H. Hart

Some of the significant facts that will affect the supply and demand for metals during the next few decades are given in this presentation. This is important because the only hope for intelligent guidance of the national destiny depends upon presenting a consistent and accurate picture of basic problems. The metals problems now fomenting are only slightly less important than those precipitating the energy crisis. Admittedly, it is difficult to generate serious thinking on this subject when the world is enjoying easy access to all metals at modest prices. This is possible because of the current world capacity to over-produce, and United States credit standing, at least up to now, has permitted buying freely on world markets. Although both these vital conditions are subject to change, there is little doubt that if the U.S. financial house is kept in order, we can muddle along for a while on a generally expanding, metal-based economy. But should our credit standing be permitted to collapse, or should there be a tightening of world supplies of metals, the nation would immediately find itself in trouble. Unfortunately, clear signals indicate that both of these conditions are threatening. The metal age started many centuries ago, and with the exception of the noble metals, barely a dent was made in world reserves until the present century. Then, as a result of the pioneering ideas of D. C. Jackling and Paul Gemmel, and the willingness of the McNeals, Penroses and Guggenheims to back ideas with money, a virtual explosion of metal production was propagated throughout the world. It is important to examine the causes of this expansion to determine whether it is a trend that may be sustained or whether it is anomalous and therefore attributable to circumstances not likely to be repeated or continued. This period of plenty is a once only phenomenon. Vast metal resources have been sitting around here for eons, while the world was unaware of or unconcerned with their existence. But when population began to grow exponentially, and ways were discovered to use metals to develop machines to do the work of men and animals, the exploitation of raw materials increased at a staggering rate. And now the realization is dawning that minerals are a wasting asset and are beginning to present supply problems that should begin to be of concern. Two main factors have caused this condition; One is the population growth, and the other is the expanding demand for irreplaceable raw materials as nations become more developed. A group of systems analysts, at Massachusetts Institute of Technology in a book Limits of Growth, has warned that at present rates of population growth and resource consumption together with environmental constraints, a point will be reached within 100 years when the world population will become totally incapable of supporting itself. The authors conclude that this end result could be avoided if a planned equilibrium could be established at a lower rate of population growth and resource consumption. Fortunately, there is evidence that the population problem is moderating. The growth rate in the U.S. has decreased from 2.3% per year in 1900 to 1.1% in 1970. But, even at the lower rate, population will double in 70 years. The world rate is greater, and if it continues, world population will rise from 3.5 billion to nearly 10 billion in 50 years. All of these projections are questionable because the dangers of growing population are now being recognized. A marked decrease in growth rate has been noted in the more developed countries-in fact, it was zero in the U.S. in 1972. The other factor affecting consumption of raw materials is the increase in per capita use of most items as individuals become more affluent. Many economists believe that developing countries such as China and India represent a vast future potential market; but there are others, with whom the author agrees, who believe over-population tends to stagnate development. Nevertheless, it is a fact that vigorously developing societies increase consumption at a rate far above their population growth rate.

Jan 1, 1974

By P. A. E. Armstrong

For hardening, the steel should be heated just above the critical temperature, as a properly forged steel quenched from this heat has some toughness, with maximum hardness and density. The quenching bath should be kept at approximately a constant temperature. In drawing or tempering, longer time periods at lower temperatures are better than the shorter periods at higher temperatures. A recent questionnaire brought out the following facts: The double-arc, double-taper bit and cross bit give the best service; resharpening of the drill steels most frequently was caused by wear of gage; chipping of bit was, with one exception, the second cause; breakage of shank was with one exception, the third cause; upsetting of bit, upsetting of shank, and breakage of body were the fourth cause. The direct cause of the necessity of resharpening given was poor heat treatment first, and faulty steel and severe rock conditions second. Rock-drill Steel By N. B. Hoffman Much of the drill steel produced in America is manufactured into hollow rods. After all forging has been finished the entire bar should be thoroughly annealed and heat trcated before the point is hardened and tempered, at least where the drill has heavy duty, such as working in deep holes and hard rock. A large number of tools of like character and doing work requiring similar properties are now being made of alloy steels; for instance a steel with a carbon content of 0.75 to 0.85 per cent., manganese 0.25 to 0.35, phosphorus under 0.020, sulfur under 0.030 and vanadium 0.18 to 0.23 has proved very satisfactory for chisels. A steel of this type properly manufactured will be far superior to the ordinary carbon steels, while at the same time is one whose price range should not prove prohibitive. Much of the cutting efficiency of a drill depends on proper heat treatment. This vanadium steel has a far greater safe hardening and forging range than ordinary carbon steels, making it more nearly foolproof. It will harden nicely at 1400" I?. but will also harden well and satisfactorily at 1550" F. retaining its quality of hardness and toughness in either case. Drill Steel from Hollow Ingots BY P. A. E. ARmstrong Hollow drill steel is made from a drilled billet with a sand-filled core or the drilled, pierced, or the drilled and pierced billet, not sand-filled, is rolled down over a projectile or ball much the same as in ordinary pipe manufacture. The first is the method generally used in this country; the second is used largely in Sweden. Swedish hollow drill steel has a

Jan 1, 1922

By Robert T. Pring

IN addition to the humanitarian aspects of a dust-control program, certain economic benefits are becoming more fully recognized and now furnish a greater incentive to the mill operator to eliminate the dust from his plant. It is well known that a favorable working environment promotes increased efficiency and improves the morale of employees, with a consequent decrease in labor turnover rates. One progressive mining company1 estimates its direct and indirect labor turnover costs at from $40 to $50 per man; for skilled labor, such as machine operators, the cost may approach $100 per man. While these figures may not be typical of every plant, they do indicate a potential savings in operating costs. Dust signifies waste; its elimination decreases maintenance costs of mechanical and electrical equipment; its recovery is often justified from the standpoint of values contained in the collected material, although in large-scale milling operations handling low-grade ore this may not be an important factor. Perhaps the most significant trend in industrial sanitation is that dust-control equipment and procedures are becoming recognized as integral parts of the mill flowsheet. Exhaust ventilating systems are now afforded equal care in design and maintenance to that given other machinery more closely related to the process. METHODS OF DUST CONTROL "Dust control" is a general term descriptive of a number of methods used singly or together to prevent particulate atmospheric contamination. These methods are, in order of their desirability, as follows: I. Change of process. 2. Isolation of process. 3. Wet methods. 4. Ventilation. a. Local exhaust ventilation. b. General ventilation. 5. Personal respiratory protection. In ore-concentration plants it is seldom practical to change a process to eliminate the dust it creates It is possible in some cases to isolate a particular dust-producing operation from the rest of the plant, provided that constant attention on the part of the operators is not required. Frequently water is used in fine crushing and fine grinding, primarily to facilitate the processing of the ore and incidentally to allay the dust produced. Wet methods, however, are not feasible in coarse and secondary crushing operations, because of the relatively great volume of water required in instantly wetting each freshly fractured rock surface. Such quantities of water would entail conveying and storage difficulties. Local exhaust ventilation is the most effective and most commonly applied control measure, wherein directional air currents through the zone of dust production draw the contaminants into a duct system. Unfortunately, only a limited amount of reliable information on exhaust ventilation is available.2-5 Of necessity these publications are rather general, being primarily concerned with engineering fundamentals. While many organizations have successfully

Jan 1, 1940

By L. M. Pidgeon, K. T. Aust

There has been considerable interest in the possible use of titanium in magnesium alloys.' Zirconium has shown some promise in this connection2 and its general similarity with titanium suggests that the latter might act in a similar manner. A literature survey revealed that quantitative data on the Mg-Ti system was unavailable. Several patents3 have claimed that titanium additions from 0.2 to 4 pct to magnesium alloys were possible, but no mention was made as to the form in which the titanium existed in the alloy. Kro114 succeeded in introducing only traces of titanium into magnesium by bubbling TiCl4 through the metal under argon or by reacting it with sodium titanium fluoride. The application of theoretical data given by Carapella5 based on Hume-Rothery's principles, involving atomic size factor, crystal structure, valency and the electro-chemical factor, suggests that a Mg-Ti alloy is a favorable case, and the system appeared to warrant experimental examination. Experimental Procedure and Results THERMAL ANALYSIS If titanium is appreciably soluble in magnesium, a change in the melting point of the magnesium might be detectable using standard cooling curve methods. Magnesium was melted in graphite crucibles under an argon atmosphere, the assembly being enclosed in a silica tube. Graphite thermocouple protection tubes served also to stir the melts. The apparatus was very similar to Fig 1, with the addition of a refractory and baffle system to prevent undue heat losses from the top of the crucible. Chromel-alumel thermocouples were calibrated using Al of 99.97 pct purity. Dominion Magnesium Limited sup- plied redistilled high purity magnesium of the analysis given above. Titanium was added in three different forms: 1. Titanium powder —100 mesh, from the Titanium Alloy Manufacturing Co., Niagara Falls, N. Y. 2. Sheet titanium from the U.S. Bureau of Mines, produced by Mg reduction of TiCl4. 3. Magnesium —50 pct titanium master alloy from Metal Hydrides Inc., Beverly, Mass. The melting point of the high purity magnesium used was measured experimentally as 651.0°C. More than a dozen tests were conducted using titanium from the three sources referred to above, in calculated additions up to 20 pct titanium, at temperatures between the melting point and 1000°C and holding periods up to 6 hr. In no case was evidence obtained of solubility of titanium in magnesium, using inverse-rate and time-temperature curves. The melting point of the magnesium was unchanged within the accuracy of measurement, namely -+0.5°C; and no other thermal arrests were detected. Metallographic investigation of the thermal analysis billets indicated that the titanium additions were apparently mechanically entrapped in the magnesium in segregated areas. Consequently, these samples were not analyzed for titanium. The master alloy proved to be a mechanical mixture of titanium particles in a magne- sium matrix. These results indicated that the titanium solubility, if such existed, could not be obtained by the usual thermal methods. X RAY DIFFRACTION INVESTIGATION In an effort to detect solubility of titanium in magnesium, samples were investigated using both the Debye-Scherrer and the Focusing Back-Reflection methods. Filings from samples of the thermal analysis billets and from pure magnesium were annealed in argon one hour at 350°C to relieve mechanical strain. Measurements made of the interplanar spacings showed no difference between the Mg-Ti samples and pure magnesium. The interplanar spacings could be measured to within 0.0002A, and the greatest variation found was 0.0004A, in the back-reflection method. The diffraction lines for magnesium were not shifted by the titanium additions indicating that the solid solubility of titanium in magnesium is of a very low order—less than 0.5 pct. From both diffraction methods, a d or interplanar spacing of 0.817A was obtained for the redistilled high purity magnesium. This latter value is not given in the standard X ray diffraction cards for magnesium metal or vacuum distilled magnesium. Theoretical calculations for a close-packed hexagonal space lattice for magnesium indicate that the planes {2134) should give a line which was found. The relative intensity for this reflection at 0.817A is slightly less than that at 0.870k for magnesium. SOLUBILITY OF TITANIUM IN LIQUID MAGNESIUM The Mg-Mn system was examined by Grogan and Haughton6 who were

Jan 1, 1950

By J. G. Balkestein, J. W. R. Baerts

During an attempt to develop a method for accurate, rapid, continuous analysis of ash content of wal, the Dutch State Mines Laboratory found that the absorption coefficient for X-rays was related to ash content. This relationship was utilized in the development of an apparatus called CendreX, used to measure the absorption and in turn the ash content. The principle, procedure, accuracy, and applications of the CendreX automatic determination of ash in coal are discussed in detail. Until recent years coal preparation research was concentrated on the possibilities and efficiency of preparation equipment. Ever increasing demands for quality in coal, however, have caused researchers to become concerned with quality control. One of the characteristics strongly influencing quality (calorific value) and, consequently, the price of coal is ash content. Both customer and producer require that the ash content be controlled. To make this possible it is necessary for the producer to collect samples from the coal stream in the washery and to determine their ash content. On the strength of the results obtained the production process can then be adjusted, if required. Until recently incineration was the only method for determining ash content. When coal is incinerated with oxygen, it takes at least 15 min to determine the ash content. Even then some time may be lost in passing on the data. Therefore, this discontinuous and time-consuming method does not make a suitable starting point for checking, re-adjusting, or modifying the production process. Since it was not possible to accelerate incineration by mechanization and automation, another type of rapid continuous analysis had to be found. This would have to depend on some coal characteristic closely linked with ash content. At the Central Laboratory of Dutch State Mines, Dijkstra and Sieswerda found that the absorption coefficient for X-rays was suitable for this purpose. An apparatus based on the measurement of this characteristic was developed. Named CendreX,* this patented equip- *A Stamicarbon N. V. registered trademark. ment, used in combination with a sampler and conditioning apparatus, permits continuous determination of ash content with satisfactory exactness to within 3 min.t At the American Mining Congress meeting of May 1961, Log A. Updegraff, surveying aspects of continuous analyaia, reported on the CendreX appartus (Mining Congress Journal, August 1961). Since the first Condition for correct ash determination, whatever the method used, is always a sample taken in the right way, some practical aspects of sampling will be discussed first. SAMPLING In coal handling operations, each grain has its characteristic properties. In both the cross-sectional and longitudinal direction of the product stream the mixture of these grains is imperfectly blended. The elimination of the factor of segregation between the cross-sections from the direction of the stream is the principal aim of continuous analysis. Therefore, the samples to be analyzed are withdrawn in various places from the segregated product stream in such a way that they form a semi-continuous flow. In order to be truly representative of the product stream, the sample flow must fulfil two conditions: 1) The sample flow must be sufficiently large to insure that adventitious differences between the composition of the product stream and sample flow will be as small as possible. 2) All grains through the entire cross section of the product stream must have an equal chance to get into the sample flow. Since there is always a segregation through the cross section the sample flow will have a bias if the sampler collects only part of this section. In order to prevent the volume of the sample flow from becoming too large, the cross sections are taken discontinuously. However, this discontinuity gives rise to the adventitious differences that arise between the composition of product stream and the sample flow, and these differences become greater and are more deranging as the fluctuations follow each other more quickly. Moreover, the intervals between the morrnents of sampling mean a delay in the analysis. The aim will, therefore, be to collect small samples, or in other words thin cross-sectional increments, taken at sufficiently high frequencies. The following points should also be taken into account: 1) The smallest dimension of the openings in the sample collector must be equivalent to at least 3 d in

Jan 1, 1962

By K. E. Beu

IN the measurement of retained austenite concentrations in steels using the integrated intensity method,1 Averbach has pointed out" that the absorption factor A(0) for a flat sample making a glancing angle 4 with the incident X-ray beam can be combined with his constant factor R to obtain our constant factor" G provided that "1—There is no preferred orientation in the sample, and 2—The geometric requirements [for the sample, film, and X-ray beam] have been met precisely."' If A(0) can be combined with R to give G according to the equation G = R . A(0) [14] then the possibility for making non-compensating errors in the austenite determination has been eliminated. This has been described previously in a technical note." Because of the brevity of the previous note,3 it was impossible to emphasize the fact that the two conditions on preferred orientation and geometry can be easily met experimentally, contrary to Aver-bach's statement that: ". . . the necessary conditions must be tested experimentally for each determination, and this is done most easily by observing whether the apparent absorption has the form of Eq. 2 [the theoretical equation for A(0)]."" he way in which these two conditions can be met experimentally will be discussed briefly to help clear up this point. In addition to these two conditions, other factors such as sample shape, homogeneity, and grain size which also affect A will be included in this discussion. A (0) depends on sample shape. The theoretical function for A was derived originally for a flat surface.' In general we have found that a flat sample surface is readily obtainable." If such a surface can * The effect of surfaces which are not flat on the measurement of retained austenite will be discussed later. be obtained, it has the following advantages: 1—it is easily reproducible from sample to sample, 2—it is the form required for metallurgical examination —this type of examination being frequently desirable for this work, and 3—it is an efficient shape for diffraction purposes. Perhaps the most important of these features is that a flat sample surface is easily reproducible; hence, this requirement on the repro-ducibility of A from sample to sample is met for all such samples. Fig. 1—Schematic diagram of the quartz crystal monochromator diffraction unit. The centerline of the main beam is at 6' to the target face. The tangent to the crystal face is at 16.8' to the moin beam. The centerline of the monochromatic beam is at 33.6 to the main beam. The sample surface can be rotated in its own plane. The angle of the sample surface and the monochromatic beam can be adjusted by rotating about the vertical axis, The film holder can also be rotated about B so that the film can be exposed over the desired angular range. For Fe K, X = 1.932A. 1011 planes of quartz have d = 3.35A. A(0) depends on homogeneity and grain size. If the sample is badly segregated or the grain size is large, the effect of micro-absorption and primary extinction1. ' must be considered. It has been shown, however, that for most plain carbon or low alloy hardened steels, neither micro-absorption nor primary extinction effects are present.' A (0) depends on camera geometry. For a given angle 0, A remains theoretically constant from a geometrical viewpoint only if the following factors are kept constant: 1—the angle of inclination .+ of the sample to the X-ray beam, and 2—the centering of the sample with respect to the film cylinder. These are mechanical problems which can be solved readily if the facilities of a good machine shop are available. The arrangement used to insure that the angle 4 remains constant and the centering of the sample is reproducible is indicated schematically in Fig. 1. The sample is clamped against a thin plate with a hole in it by means of a spring-loaded pres-

Jan 1, 1954

By Anthony Folger, Howard R. Lowe, J. F. Dougherty, E. G. Trostel, Joffre Meyer

The status of the natural gas industry in Alberta, Canada, is described with particular reference to the current extent of natural gas reserves and possibilities for additional development. Certain major fields are discussed as representative of the types of gas accumulations within various broad geographical divisions of the provinces. The estimation of the future performance of a gas reservoir is discussed as the basis for an estimate of the future availability of natural gas from presently known reserves. The future availability of the provincial reserves and the estimated future demand for gas within the province are described. INTRODUCTION This paper is a condensation of a detailed study of the natural gas reserves and the future availability of pipeline gas in the province of Alberta as prepared for Trans-Canada Pipe Lines Limited and presented in public hearings at Edmonton and Calgary before the Petroleum and Natural Gas Conservation Board of the Province of Alberta. The study began in October, 1950, and resulted in the preparation of five volumes of data at the expenditure of more than 20,000 man-hours. This paper is designed to afford a broad picture with detail limited to a type example of both natural ga-accumulation and future availability of gas supply. The province of Alberta has an area of 255.285 square miles which, for sake of comparison. is 8,359 square miles smaller than the state of Texas. Natural gas was first discovered in 1883 at the now abandoned Alderson well located some 20 miles southeast of the town of Princess. The first gas in commercial quantities was found at Medicine Hat in 1890. During the last 68 years. 187 localities have been discovered which are capable of gas production, and 73 per cent of these have been found since 1945. Sixty fields currently are producing gas, including 22 non-associated gas accumulations. Location of the oil and gas fields and prospects in the province of Alberta is shown in Fig. 1, together with a list of the localities of measurable gas, Fig. 1A. The estimated total provincial gas reserve as of Jan. 1, 1952, for the 104 fields estimated, is 11.7 trillion cu ft proved and probable, and for the 187 known areas capable of production is in excess of 16 trillion cu ft on a total proved, probable, and possible basis. Five fields (Pincher Creek, Leduc-Woodbend, Viking-Kinsella, Cessford and Medicine Hat) are estimated to have recoverable reserves of more than one trillion cu ft each. A sixth field, Turner Valley, was initially in this group, but its reserves have been depleted substantially. Twenty-four fields, of which the above mentioned six fields are a part, have estimated gas reserves (including the possible category) in excess of 100 billion cu ft. These 24 fields account for 79 per cent of the total provincial reserves. Comparative systemic analyses reflect that 56 per cant of Alberta's gas reserves are contained in sediments of Cretaceous age; 30 per cent in sediments of Mississippian age; 10 per cent in sediments of Devonian age; three per cent in sediments of Triassic age; and the remaining one per cent in Jurassic and Permo-Pennsylvanian sediments. It is expected that the relative importance of the Mississippian, Devonian, and Triassic sediments will be increased as exploration progresses. GENERAL GEOLOGY The western Canada basin comprises the sedimentary area between the Canadian Shield and the Rocky Mountain Front Range, the Arctic Ocean, and the International Boundary. The basin has an approximate area of 765,000 square miles and embraces parts of the provinces of Manitoba. Saskatchewan. Alberta, British Columbia and the Northwest Territories. Generalized columnar sections for the Province of Alberta are shown in Fig. 2. Substantially all of Alberta, except its northeast corner, has sedimentary cover. Sediments of all the geologic systems are represented. except those of Silurian age.

Jan 1, 1952

By J. A. Herbst, D. W. Fuerstenau

This paper examines the zero order production phenomenon in the context of the size discretized batch grinding model. A restrictive interrelationship between the selection and breakage parameters of the model, which is mathematically sufficient to ensure zero order behavior, is delineated. Based on this interrelationship, a scheme is developed for predicting the values of the selection and breakage parameters for all size fractions from a minimum of experimental data. To test this scheme, dolomite was ground in a laboratory batch ball mill. Successful simulation of the comminution behavior of this system was achieved using the batch grinding model with the parameter values obtained from the proposed scheme. Historically, a preponderance of comminution research has centered on attempts to relate breakage energy to the performance of comminution machines. Concomitantly, grinding data were interpreted almost exclusively in terms of inherently empirical energy-size reduction relationships1-3 or "laws of comminution"4- 6 which were based on highly oversimplified descriptions of the fracture process. In some instances, these relationships provide a crude basis for the correlation of experimental data, but, invariably, this approach is inadequate for meaningful process simulation. The control and optimum design of comminution circuits require a mathematical model capable of depicting the size reduction behavior of every size fraction for grinding conditions of technological importance. Energy-size relationships do not provide this detailed information. For example, an energy-size analysis for batch ball-milled dolomite has recently been completed in the authors' laboratories.7 This analysis provided a satisfactory correlation between the hypothetical size modulus, which characterizes only the finer portion of the size distribution, and the input energy. However, this relation did not constitute an adequate description of the complete system. In general, one of two distinct viewpoints toward simulation has been adopted in recent comminution research. The first approach focuses on the fracture of single mineral specimens, with the essential aim of representing the over-all process in terms of the breakage characteristics of individual particles and the characteristics of the stress field which the particles experience within the particular size reduction device. As illustrated by Harris's review,' the actual incorporation of single-specimen fracture information into a description of the behavior of a multiparticle comminution system has seldom been attempted. The only model to accomplish this incorporation was the one developed by Schönert.8 The Schonert model treats single-passage grinding machines in terms of a distribution of effective loads acting on a particle, a distribution of required particle breakage energies, and the breakage product distribution. However, the use of single-particle fracture behavior to derive models of the size reduction process is at present limited to machines in which the particle residence time is approximately equal to the time required to apply stress. As a result, Schönert's analysis cannot be used to advantage to simulate the complex environment which prevails within a tumbling mill. For multiple-passage systems a second approach to the description of comminution processes has been more fruitful. This approach entails the formulation of a mathematical model which is phenomenological in nature in that it lumps together the entire spectrum of stress-application events which prevail in a system under a given set of operating conditions. The appropriately defined average of these individual events is then considered to characterize the over-all breakage properties of the device. Thus, to analyze the performance of a tumbling mill, the manner in which the particles of a particular size (or size fraction) are stressed need not be distinguished. Instead, a single parameter is assumed to represent the resistance of that size to fracture, given the average grinding environment which exists in the mill. The isolation of such a parameter and a related set of quantities, which constitute the breakage product size distribution for the average event in this size fraction, allows the formulation of physically meaningful descriptive equations capable of yielding precise and detailed information for simulation.

Jan 1, 1969

By J. C. M. Li

The steady state shape of a shrinking cylindrical grain boundary of miform boundary energy is shown to be circular. This is based on the principle of either the minimum rate of entropy production or the minimum thermokinetic potential. The circular shape corresponds also to a state of minimum (not maximum) velocity. The steady state shape of a grain boundary moving between two inclined surfaces is a circular cylindrical arc whose position and curvature will be afjected by the nature of the surfaces. The minimum thermokinetic potential is the only valid criterion in this case. THE preceding paper1 reports an interesting experiment in which it is shown that a grain boundary moving between two inclined surfaces assumes a circular cylindrical arc whose axis nearly coincides with the line of intersection of the two surfaces. The driving force is well defined since it is the energy of the grain boundary itself. The velocity of the grain boundary is found not to vary linearly with the driving force. Several interesting questions arise: 1) What principle determines the shape of a moving grain boundary? 2) What is the effect of the inclined surfaces? 3) How do we understand the nonlinear velocity-driving force relationship? It is attempted in this paper to discuss the first two questions based on irreversible thermodynamics and in a following paper to discuss the third question based on dislocation theory. STEADY STATE SHAPE OF A SHRINKING LOOP (A CYLINDRICAL GRAIN BOUNDARY) In irreversible thermodynamics, there are two criteria for the steady state. One is the minimum rate of entropy production2 which is based on the symmetry of phenomenological coefficients and is applicable to linear force-flux relations with constant coefficients. The other is the minimum thermokinetic potential3 which is based on the integrability of a certain Pfaffian differential equation and is applicable to nonlinear systems with variable coefficients. In the case of a shrinking grain boundary loop (a two dimensional version of a cylindrical grain), the flux of atoms across the grain boundary can be taken as the local boundary velocity v measured perpendicular to the boundary (the number of atoms transferred per unit area per second is equal to the product of atom density and the velocity of the boundary). The local thermodynamic driving force can be taken as y/p with y being the grain boundary energy (invariant with respect to the orientation and curvature of the grain boundary) and p being the radius of curvature. Such driving force can be understood by considering the loop as an elastic string with tension y. As shown in Fig. 1, across a length ds along the loop, the direction of y changes by an angle d@ which is ds/p. Because of this change of direction, the tension exerts a force perpendicular to the curve equal to yd@. The force per unit length is then y/p. According to the experimental observation, the velocity v is a power function of y/p, where M is the velocity at unit driving force and 'n is a constant. The rate of entropy production per ds along the loop is vyds/pT, where T is the temperature. For a given length L of the loop, the total rate of entropy production is The thermokinetic ptentia13 has only a differential definition and its existence depends on the integrability of this definition. In this case, Eq. [3] happens to be a total differential and the thermokinetic potential can be defined as which turns out to be the same as the rate of entropy production, Eq. [2], except for a constant factor n + 1. Strictly speaking, since the flux-force relation is not linear, the rate of entropy production may not be a minimum at the steady state. However, because of the proportionality between Eqs. [2] and 141, the state of minimum thermokinetic potential happens to be the same as that of minimum rate of entropy production. The steady state shape thus can be obtained by minimizing either integral [2] or [4] for a given L.

Jan 1, 1970

By K. C. Hong, R. B. Jensen

The problem of determining the optimum set of steam volumes and cycle lengths for a single well undergoing multicycle steam stimulation in order to maximize the cumulative discounted net income has been formulated mathematically and programmed for a digital computer. The mathematical fonnulation of the problem and the method for its solution are discussed in this paper. The oil production performance during each stimulation cycle was simulated by either a constant percentage or a harmonic decline. Using simple analytical expressions for production performance, the cumulative discounted net income and cumulative time of operation were related to the pertinent process and cost parameters and two principal process control variables (cycle length and steam injection volume). The discrete maximum principles was used to transform the equations for cumulative time of operation and cumulative discounted net income into a set of simultaneous equations. The simultaneous equations then were solved by trial and error on a digital computer to determine the set of cycle lengths and stem injection volumes that gives maximum cumulative discounted net income over the project life. INTRODUCTION Steam stimulation is a process for improving the oil recovery rate from wells producing high-viscosity crudes. The process is applied on an individual well basis and is executed in a series of cycles, each consisting of three phases: steam injection, soaking (steam condensation), and production. Significant increases in production rate following the stimulation operation result from heating the reservoir around the wellbore. As heat is removed with produced fluids and dissipated into nonproductive formations, the production rate declines, usually to near the prestimulation value. Typical production responses are given in case histories reported by Owens and Suter,l and are depicted in Fig. 1. Duration of the production phase is equal to the time for the oil production rate to decline to some specified value and is called the cycle length. (Cycle length is defined as the producing portion of the cycle and does not include the downtime required for steam injection and soaking operations.) Termination of the production phase coincides with the start of steaming for the next cycle. The process is continued, cycle by cycle, until it becomes unprofitable. Models 2-4 have been developed to simulate behavior of a single well during one cycle of steam stimulation and have been used to investigate the effects of system and operating conditions on the production responses. However, these investigations have not shown how the models can be used to determine a most profitable set of operating conditions for a multicycle stimulation project. Perhaps these models are too complicated mathematically to be adapted readily to an optimization study. This paper presents a method for optimizing a multicycle steam stimulation project based on simple production performance models. First, the performance of a steam-stimulated well during each cycle was simulated by either a constant percentage or a harmonic decline model. Using these simple analytical expressions for production performance, the cumulative discounted net income (before tax) and cumulative time of operation for each cycle were related to the pertinent process and cost parameters and two process control variables—the cycle length and the steam injection volume. Finally, the profit function to be maximized was formed. The analogy between the above problem and problems of optimizing multistage decision processes that have been reported extensively in the chemical engineering literatures5-10 in recent years has led this investigation to the use of the discrete maximum principle.5-7 This principle was used to transform the equations for cumulative discounted net income and cumulative time of operation into a set of simultaneous equations characterizing the optimum operating conditions in terms of the two control variables. These equations

Jan 1, 1970

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

By D. S. Rowley, F. C. Appl

Assuming that rock behavior, during cutting with a single diamond, may be approximated by that of a rigid, Coulomb, plastic material, a theory of single diamond cutting action has been developed. Using this theory, the stresses on the diamond cutting surface and the components of the cutting force have been determined. Theoretical results agree reasonably well with available experimental data. The theory of cutting of single diamonds may be used as the basis for subsequent study of the perfonnance of surface set diamond drill bits and other surface set diamond cutting tools. INTRODUCTION For more than twenty years, surface set diamond bits have been used successfully in the mining and petroleum industries to drill and core rock formations that range from medium hard to the hardest known formations. Most extremely hard rock formations cannot be economically drilled or cored by any other means. In view of the growing use and importance of surface set diamond drill bits, it is reasonable to study the way in which these tools cut, and the factors that influence wear of the diamonds. Such knowledge will contribute to better bit design and will improve operating procedures. To analyze the cutting performance of these tools it is appropriate to consider the way in which an individual diamond cuts. Once this is established, the over-all performance of the bits can be determined by considering the total effect of the individual diamonds. In recent years there has been a growing interest in rock mechanics and there now exist several publications dealing with the deformation and failure of rocks. Notable experimental work has been reported by Bredthauer,1 Handin and Hager,2, 3 and Gnirk and Cheatham.4 An extensive collection of data pertaining to rock properties at low confining pressures has been given by Wuerker.5 Cheatham and Gnirk have recently presented an excellent review of the state of knowledge regarding analytical and experimental rock deformation and failure.6 Generally rocks are extremely weak in uniaxial tension, and weak or only moderately strong in uniaxial compression. Both tensile failure and compressive failure are generally brittle in nature. This means that there is little or no deformation or "flow" of the material before shear or tensile fracture occurs. Thus, until fracture occurs, rock behaves very nearly like an elastic material in uniaxial stress. Significant changes in behavior of rock occur under conditions of triaxial compressive stress. There is generally a marked increase in compressive strength and in ductility. It has been demonstrated that the failure becomes plastic (in a macroscopic sense) at sufficiently high values of confining pressure. Sharp wedge chisel indentation studies conducted by Gnirk and Cheatham indicate that many rocks behave in a plastic manner at relatively low triaxial compressive stress states.4 If "failure" under triaxial compressive conditions is considered to be either complete rupture or macroscopic plastic flow, then the general failure characteristics of a rock can be reasonably well represented by the commonly known Mohr envelope. This certainly is not a perfect failure criterion (since the effect of the intermediate principal stress is neglected) but it has been found to be adequate for most engineering purposes. Mohr envelopes usually are constructed graphically using experimental triaxial test data. For purposes of analysis it is convenient to represent the envelope in equation form. Among the several approximate forms appearing in the literature, a parabolic form is suggested by Cheatham,7 and an exponential form is suggested by Paone and Tandanand.8 The exponential form has been adopted for this study, and based on published data, appropriate parameters have been established for 19 rock types. A typical plot of the data compared with the approximate envelope, and a summary of the rock properties and

Jan 1, 1969

By L. Valentik

Many attempts have been made during the last 40 years to evaluate the performance of gravity separation equipement, that is, the effectiveness with which light and heavy particles are separated. The most comprehensive treatment of the subject was made by Cerchar at the 1st International Conference on Coal Preparation held in Paris in 1950. The methods suggested by the Conference were accepted and very widely used in the last two decades. This paper discusses an improved method of evaluation in the light of the now-accepted standard presentation. The float-and-sink analysis of the product is presented on a Gaussian distribution curve, resulting in an easier visualization of the inherent difficulties of separation. The ogives of the distribution curve me then plotted, giving a quantitative measure of the deviation from perfect separation as an error distance instead of an error area. Illustrations of the new method are given both for gravel and for coal preparation, but the content is valid and applicable to other types of minerals which are separated by gravity methods. Many attempts had been made during the last forty years to evaluate the performance of heavy-media separation (HMS) equipment, that is, the effectiveness with which floats and sinks are separated.'-' The most comprehensive treatment of the subject was made by Cerchar at the 1st International Conference on Coal Preparation held in Paris. 6 The primary aim was the thorough understanding of the mechanism of separation and the unified presentation of data on gravity separation so that the evaluation and comparison of washery performance could be made from all over the world. No strict overall standardization has been achieved, but after the conference a more or less uniform presentation of performance was accepted, which, during the last two decades, has been very widely used. In this paper, illustration of the old methods and an improved method of evaluation will be given. HEAVY-MEDIA SEPARATION (HMS) PERFORMANCE CRITERIA In the ideal HMS process, all material lower in density than the specific gravity of separation (SGS) would be recovered as floats and all material of higher density would appear as sinks. In order to evaluate the misplaced material, the washery products are tested at the density at which the washing unit is operated. The original type of plot1,7, 8 is shown in Fig 1; this was developed primarily for coal cleaning units. The curve for raw coal represents the cumulative percentages of sink material. The refuse curve is also plotted as a cumulative sink, the percentages being expressed in terms of raw coal. This diagrammatic representation of the results of washing units has the merit of easy visual observance of the degree of separation obtained. The error areas (cross-hatched) are a measure of the amount of misplaced material and therefore they can be used to characterize the quality of separation. The ideal and actual separating performance between floats and sinks can be best seen from the partition curve developed by Tromp,2 where the ordinate is the percentage recovery of the sinks, and the abscissa is the specific gravity (Fig. 2). It can be seen from the shape of the curve that as the SGS is approached, the proportion of material reporting to the improper product increases rapidly. In fact, the SGS can be defined as the density of the material in the feed that is distributed equally between float-and-sink products. When the upper half of the curve is inverted, a shape similar to that of a Gaussian error distribution curve is obtained and therefore the analysis of gravity separation may be carried out by using the law of probability. The shape of the curve in Fig. 2 is determined partly by the density composition of the feed, and partly by the sharpness with which the unit separates floats from the sinks.9, l0

Jan 1, 1970

By C. R. Kyle, R. L. Perrine

A transparent model of a reservoir has been used to study some characteristics of instability in miscible displacement. The linear model dimensions are 1/4 in. x 91/2 in. x 10 ft. The model is packed with spherical glass beads. Thee groups of experiments have been performed. The objectives were to measure, respectively, the rate of growth of the transition zone, flow velocity variations in the transition zone, and the effect of a graded viscosity zone on stability. All experiments were compared, where possible, with theory. The transition zone grew almost linearly with distance traveled, regardless of flow rate, where adverse viscosity ratios were used. At very adverse viscosity ratios and large distances traveled, some reduction below linear growth was noted. This could be attributed to the effects of mixing. General similarity in flow pattern was commonly shown in different tests, although exceptions occurred at the higher viscosity ratios. Injection of tracer spots permitted direct experimental measurement of velocity variations. Statistical methods were used to compare observed velocity variations with recently published theories. Surprisingly good agreement with some theoretical predictions was obtained. In the experiments using an initially graded viscosity zone, macroscopic stability was reached before predicted by theory. Under conditions theoretically considered to be slightly unstable, any fingering tendency was too slight to become observable within a 10-ft long system. The general correlation of all experiments with published theory was good, and suggests that theoretical predictions can be extended to reservoir problems. INTRODUCTION Early laboratory studies of miscible displacement demonstrated the high recovery efficiency possible with this method. Linear laboratory models showed that, under some circumstances, all in-place hydrocarbons could be recovered using as little solvent as 5 per cent of the pore volume. These results led to a series of pilot field projects. Under realistic conditions, however, other laboratory studies showed that a small solvent bank may not recover much more oil than a conventional gas drive. The cause of this lack of efficiency is unstable viscous fingering. The size of the solvent bank required to give optimum recovery is, therefore, a question of great economic significance. The object of the experiments described in this paper was the quantitative measurement of unstable flow parameters, the verification of present theories on the miscible displacement process, and correlation of these theories with ex peri mental observation. Of the theories which have been advanced, those by Dougherty, Koval and Perrine show promise of predicting reservoir performance with reasonable accuracy.l-7 The present experiments were correlated, where possible, with the theories of Koval and Perrine. Dougherty's theory was not used because of the additional computational difficulty it presented and the belief that no further information would result. EXPERIMENTAL EQUIPMENT A transparent reservoir model, consisting of a vertical reinforced plexiglass column, was used for the experiments. The column was packed with glass beads, which served as the porous medium. To induce a known velocity disturbance in the flow, a double cosine wave restriction in the transverse cross-section was placed at the top of the column. To mark the flow field and provide a means of measuring the local fluid velocity, a dye-spot injection system was provided. The column was 10 ft high by 1/2 in. wide by 1/4 in. deep. The cosine restriction was placed 16 in. from the top of the column. The glass beads were smooth and spherical and had a mean diameter of 0.0102 cm. Liquids entered the top of the column through a manifold allowing three points of entry (left, center, and right, or any combination of these). A positive-displacement pump with variable-speed drive was used to control liquid flow rates. The pump transferred viscous oil from a reservoir to an accumulator, which displaced the test liquid into

Jan 1, 1966

By Seymour G. Epstein

Using a modified capillary-reservoir technique, electromigration of dilute solutions of silver in liquid bismuth has been measured with relatively good precision. The effects of experiment duration, temperature. current density, and silver concentration have been investigated. Chemical diffusion coefficients of silver in liquid bismuth were also measured at temperatures ranging from 300°to 600°C. The effective valence of silver in bismuth was calculated as a function of temperature from a comparison of electric mobilities and diffusion coefficients. In an alloy containing 1 wt pct Ag, the electric mobility of silver increased from 1.65 x X sq cm per v-sec at 300°C to 2.38 x 10-4at 600°C; the diffusion coefficient in-creased from 3.0 to 17.5 x 10-5 sq cm per sec over the same temperature range. Calculated values of effective valence decreased from 0.28 at 300°C to 0.10 at 600°c. ALTHOUGH there has been considerable progress in the theoretical treatment of electron-transport properties in liquid metals, the mechanisms of mass-transport phenomena in liquid metals are still not clearly understood. This is especially true for the case of electro migration, alternatively termed elec-trotransport or electrodiffusion, which is mass transport induced by an applied electric field. A thorough knowledge of the mechanisms governing electromigration will considerably aid in understanding the electronic state of an impurity atom in a liquid metal. Electromigration has been long observed and studied in liquid metals and alloys. However, no satisfactory theory to explain the observed effects has been developed. The disparity in the present theoretical treatments, summarized by Verhoeven,1 has been attributed to the difficulty in describing the momentum transfer between electrons and ions and to the lack of precise measurements in liquid metals, especially at elevated temperatures. Prior to the last decade most of the electromigration studies were qualitative, in that only the direction of migration of alloy constituents was determined with any degree of reliability. These results have been summarized by schwarz,2 who was able to measure the electric mobility of several elements in mercury. More recently electromigration in liquid metals has been measured by a variety of techniques, with a varying degree of success. Mangelsdorf3,4 made precise measurements on dilute amalgams at room temperature, using a technique relating changes in composition to changes in alloy resistivity, but was unable to make measurements at elevated temperatures. Using a modification of this technique, Verhoeven and Hucke5 measured electromigration and resistivities in liquid Bi-Sn alloys. However, the resistivity technique is not sensitive to small composition changes and is impractical for very dilute alloys. Verhoeven and Hucke6 also measured electromigration of several solutes in liquid bismuth by adapting the capillary-reservoir method for determining diffusion coefficients in liquids. The reported precision of these measurements was poor, however, primarily due to the large uncertainties in the chemical analyses to determine concentration changes. Belashchenko7 has summarized the recent Russian investigations of electromigration, many of which, however, are of questionable accuracy. The present study was initiated to develop an experimental technique which would be both versatile and sufficiently sensitive to yield precise measurements of electromigration of solutes in dilute metal alloys at elevated temperatures. Using this technique, a comprehensive study of silver in liquid bismuth was made to determine the effects of experimental variables on the apparent electric mobilities. Chemical diffusion coefficients of silver in liquid bismuth were also measured over the same temperature range for comparison with the electromigration data. EXPERIMENTAL TECHNIQUE Electromigration Measurements. Electromigration of silver in liquid bismuth was measured by the capillary-reservoir technique, similar to that used by Verhoeven and Hucke,6 but modified to yield more

Jan 1, 1967

By R. E. Collins

The existence of fluid migration across fixed boundaries in oil and gas reservoirs has been known for many years. Several techniques have been developed in the past for estimating The rate of migration across fixed boundaries as an aid in planninng field development and in the valuation of oilfied properties. The principal de/errc7nt to the use of these techniques lies in the rather extensive reservoir and field data required for ca1cula1ion.s of fluid migration. For this reason, a new, simplified procedure has been developed which makes possible the calculation of fluid migration with a minimum of field and resrvoir data. This new technique is based on certain. solutions of the differential equations describing flour in the reservoir which assume, for the portion of the reservoir of interest, that the formation can be approximated by a homogeneous rock of uniforrn thickness, that only a Single mobile fluid phase exists, and {hut fluid production at the well is solely a result of expun.rioti of rile resersoir fluds. The results of the, present work are compiled in a set of curves. These curves can he used to calculate both rule and cummulative fluid migration when the abovc assumptions ore ju.r/ifiril. The only data required for such calcu1ations are the production hisrories of all wells in the field, the permeability and porosity of the reservoir., the, compressibility and viscosity of the fluid. and the shape of the reservoir, INTRODUCTION The migration of fluids across fixed boundaries in oil and gas reservoirs has long been recognized as an engineering and economic problem, but no methods for estimating the extent of migration during the development stage of a reservoir have been published. The investigation reported here has been directed toward providing a simple technique for estimating the extent of such migration and has therefore been restricted to the simple case of a homogeneous reservoir of uniform thickncss containing compressible liquids. It is assumed that only a single mobile fluid phase exists and that fluid production at the wells is solely by expansion of the reservoir fluids. Obviously, few, if any. reservoirs conform to these assumptions during their entire productive life. On the other hand, most reservoirs approximate fluid expansion reservoirs during their initial stages of primary production. Consequently, the present work should be applicable during the field development of most reservoirs, regardless of whether or not they ultimately are gas cap, dissolved-gas, or water-drive reservoirs. The mathematical analysis of this problem has been outlined in the Appendix, while the results of the investigation are presented in the following discussion. DISCUSSION OF CALCULATION PROCEDURE SLNGLE Well, Ini-iimite Reservoir The procedure for calculating fluid migrations is based on solutions of the partial differentia1 equations describing the flow of a homogeneous compressible liquid in a homogeneous reservoir of uniform thickness. This differential equation has the form of the well-known diffusion equation. The equation, as applicable to our problem, is where p is fluid density, is porosity, EL is viscosity, c is compressibility,* and k is permeability; .r, y and t are the space coordinates and time. Derivation of this equation is given in the Appendix. The analytical solution of this equation for a single well of negligible radius producing at a constant rate. q, from a reservoir of infinite areal extent for a time, 1. can he readily obtained. From this solution the rate of flow and also the cumulative flow across a straight line segment of length, 1, at a perpendicular distance. 6. from the well can be computed. One end of the line must be on the perpendicular joining the well to the

By J. S. Kirkaldy, D. H. Weichert, G. R. Purdy

Two-phase diffusion couples have been used to simulate the growth of proeutectoid ferrite in ternary Fe-C-Mn austenites. It has been shown, theoretically and expermentally, that the results fall into two classes: a high-super saturation class in which the major role of manganese additions is to influence the boundary conditions for carbon diffusion; and a low-supersaturation class in which the partition of manganese is required. In the latter case, a drastic inhibition of the reaction rate is to be expected. As an aid to the kinetic analysis, a portion of the iron-rich comer of the Fe-C-Mn constitution diagvam has been determined. The conclusions drawn from this work have a direct bearing on the kinetics of the grain boundary ferrite precipitation reaction and thus yield insight into the manner in which alloying elements can influence the rate of austenite-decomposition reactions. THE role of alloying elements in the austenite-decomposition reactions has provoked considerable interest, since it is apparent that an understanding of this phenomenon will yield insight into the harden-ability problem. In the present investigation, attention is focused upon the proeutectoid-ferrite transformation in the system Fe-C-Mn, and upon the manner in which manganese additions affect the growth rate of ferrite. When hypoeutectoid austenite is supersaturated, the ferrite first formed usually exhibits two distinct types of morphology. At low super saturations, grain boundary layers grow into the austenite grains with an approximately planar interface, and usually possess at least one incoherent phase boundary. At high supersaturations, Widmanstiitten plates appear, which bear an orientation relationship' to the parent austenite. In this case, there is a chance of partial lattice matching along the sides of the plates and an attendant semicoherent interface structure. Purdy and Kirkaldy2 have used a two-phase binary Fe-C diffusion couple to demonstrate that carbon volume diffusion controls the incoherent reaction, while Rouze and rube,' using thermionic-emission microscopy, have shown that the thickening of Widmanstatten ferrite plates is appreciably slower than expected for carbon-diffusion control. This suggests that the plates are bounded by partially coherent, low-mobility interfaces. The redistribution of alloying elements during transformation has been the object of studies by Aaronson4 and owmman,5 who have shown that no alloy partition occurs during ferrite precipitation in the systems Fe-C-Cr and Fe-C-Mo, respectively. More recently, Aaronson et al.6 have shown that some manganese partition occurs at low super-saturations in the system Fe-C-Mn, but that no partition occurs at higher super saturations. Pickle-simer et al.7 observed that no manganese partition occurred during the early stages of the pearlite transformation in a manganese steel, and concluded that volume diffusion of the alloying element is not the rate-deter mining factor. The diffusion coefficients pertinent to this investigation have been measured by Wells, Batz, and Mehl8 (carbon in austenite), R. P. smith9 (carbon in ferrite), Wells and Mehl 10 (manganese in austenite), and Kirkaldy and Purdy11 (diffusion of carbon on a manganese gradient in austenite). Kurdjumov 12 has shown that the diffusivity of substitutional elements in ternary austenites up-quenched from martensite may be greatly enhanced, due, apparently, to the presence of a persistent defect structure. The recent work of Krauss 19 showing high densities of tangled dislocations in reversed Fe-Ni martensite is in agreement with this conception. THEORETICAL Diffusion in ternary or higher-order systems may be described with the aid of Onsager's extenbion of Fick's first law,14 in which the flux of each of the n components is assumed to be a linear function of all concentration gradients:

Jan 1, 1964

By I. R. Kramer, H. Shen, S. E. Podlaseck

The tensile and creep properties of aluminum in vacuum have been investigated. It was found that the general effect of a vacuum environment was to reduce the rate of work hardening. Results obtained from creep tests showed that lowering the test pressure from 2 x 10-4 to 10-7 torr produced a decrease in the activation energy as much as 500 cal per mole. An attempt is made to explain these effects in terms of how the surface-stress field of a specimen may be affected by a vacuum environment during plastic deformation. In a previous paper,' the results were reported of some of our early work on the effect of vacuum environment on the stress-strain curve of aluminum single crystals. This effort has been extended to the studies of the tensile and creep properties in vacuum as a function of various metallurgical parameters. Some of the recent surface-effect studies2'3 have revealed that a region of high dislocation density, the so-called "debris" layer, is formed near the surface of the specimen as a result of plastic deformation. This layer acts as a surface barrier to oppose dislocation movement. The strength of this barrier depends on the surface condition such as oxidation or surface removal. Experimental results obtained from surface-removal work2, 3 indicate that such a surface barrier, which may be characterized by a stress field, affects the applied stress and the rate of work hardening. In the case of aluminum, this stress field was found to be directly proportional to the strain and the strain rate; however, the slope of this curve is independent of orientation of the crystal and may be altered by using different surface treatment. Since the escape of dislocations may be retarded by the presence of an oxide on the surface of a specimen, it is expected that a change in the rate of oxidation in vacuum will affect the process of dislocation accumulation in the debris layer. Consequently, it also affects the plastic behavior of a metal. This paper reports the changes in some of the creep and tensile properties of aluminum in vacuum and discussions of the observed effects in terms of the concept of the "debris" layer. EXPERIMENTAL PROCEDURE Tensile Tests. A sketch of the tensile apparatus is given in Fig. 1. This apparatus was contained in a bell jar (14 in. diam by 24 in. high) connected to a 10-in. vacuum system. The load was applied to the specimen by means of a gear train which was driven by a magnetic clutch located outside the vacuum chamber. The specimen, held by a pair of square shoulder grips, was attached to the load cell at the top and the drive gear at the bottom. A displacement transducer was placed between the two grips as shown in the figure to measure the elongation. Signals of elongation and load were amplified and recorded on an X-Y recorder. The system was capable of detecting loads as small as 0.025 lb and displacements of 0.0002 in. Shoulder-grip specimens of aluminum single crystals, having a nominal square cross section of 1/8 by 1/8 in. and a 3-1/2-in, gage length, were grown by the Bridgeman techniques. The original purity was 99.997 pet. The orientations of the crystals investigated are shown in Fig. 4(a). The crystals were annealed at 600°C for 2-1/2 hr, electropolished, and placed in the vacuum test chamber without any delay. All the crystals were deformed at a strain rate of 4 x 10-5 sec-1 at 24o ± 3°C. A study was made to find whether a chemically passive surface film would give the same effect as a vacuum environment. Specimens of aluminum 1100 (0.187 in. diam with a grain size of 0.1 mm)

Jan 1, 1965

By L. V. Pirela, S. M. Farouq Ali

Some interest has been expressed recently in the application of solvents in conjunction with a thermal drive, such as a steamflood. At least one field project of this type has been reported. This paper makes the first attempt to provide some of the basic information necessary for choosing a solvent for such an application. Results of displacements conducted at elevated temperatures are also discussed. This paper shows that, in the case of alcohol-hydrocarbon-water or brine ternary systems, the system miscibility may increase, decrease, or both increase and decrease within the same system when the temperature increases. The distribution coefficient was consistently found to increase in favor of the oleic phase with an increase in temperature, which is advantageous from the standpoint of oil recovery. Results of solvent displacements in a sandstone core showed that even a relatively small temperature effect in the favorable direction (increase in miscibility and distribution coefficient) can lead to a 50 percent increase in oil recovery. On the other hand, if the system miscibility decreases with the temperature, even though the distribution coefficient increases, the oil recovery at the higher temperature may not increase. INTRODUCTION Miscible displacement has been the subject of many investigations. Miscible-phase solvent flooding, employing solvents such as alcohols that are miscible with both oil and water, has received considerable attention. Investigations conducted by Gatlin and Slobod,l Taber, Kamath and Reed,2 Holm and Csaszar,3 and Farouq Ali and Stah14 have helped in understanding the mechanism of solvent flooding. While the use of alcohols and similar solvents as oil recovery agents is economically unattractive, these solvents nevertheless provide a means of understanding the mechanistic aspects of important miscible-phase oil recovery processes such as the Maraflood process (discussed by Gogarty5). As shown by Taber et a1.,2 the phase behavior of a solvent-oil-water system is of .utmost importance in determining the efficiency of the oil displacement. This paper makes the first attempt to obtain the ternary phase behavior data for nine alcohol-hydrocarbon-water/brine systems at elevated temperatures. Results of core tests at elevated temperatures are also presented which corroborate the effect of temperature on oil recovery, as judged on the basis of phase-behavior data. The use of solvents at elevated temperatures has been suggested earlier by Farouq Ali.6 At least one field test of this type has been reportedO7 With the widespread use of thermal recovery techniques, it is possible in some situations (especially in steamflooding) that the use of a suitable solvent in conjunction with the heat carrier may be economically feasible. This paper attempts to provide some of the basic information needed for judging such feasibility. LOCATION OF THE PLAIT POINT The phase behavior of a typical ternary system consisting of a solvent, hydrocarbon and brine (or water) can be represented by a triangular diagram such as the one shown in Fig. 1 (for temperature TI). Point Pon the binodal curve represents the plait point, being the limit of tie lines such as Y1 Y2 The compositions of the coexisting oleic and aqueous phases are given by points Y2 and Y1, respectively, for any mixture composition along Y1Y2. The characteristics of ternary diagrams have been discussed by Findlay8 and others. Taber et aL3 have shown that the position of the plait point in a particular ternary system plays the decisive role in determining whether or not theoleic phase would be displaced in a continuous manner during an alcohol displacement. The area above the binodal curve also is important, since it represents

Jan 1, 1969

By R. I. Jaffee, E. S. Bartlett, D. N. Williams

The oxidation resistance and fabricability of molybdenum powder-metallurgy alloys containing up to 20 wt pct nickel in the form of a fine dispersion were studied. The effects of dispersion distribution and of amount and type (pure nickel or nickel compounds) of additive were considered. A definite improvement in oxidation resistance was observed, but the amount of improvement fell far short of requirements for an oxidation-resistant alloy. Fabricability by hot-rolling was limited. INVESTIGATIONS at Ohio State university1 and Battelle Memorial institute2 have indicated that the attainment of a truly oxidation-resistant molybdenum-base alloy for high-temperature service, with the coincident retention of high-temperature strength and toughness, will be a difficult, if not impossible, feat. Among the most promising alloy systems studied was the molybdenum-nickel system shown in Fig. 1. Alloys in this system show good oxidation resistance at temperatures well above the normal melting point of molybdenum trioxide because of the regenerative formation of protective nickel-molyb-date (NiMoO4) on the surface of the alloy during exposure at high temperatures. Unfortunately, the required alloy content to obtain oxidation resistant molybdenum-nickel alloys far exceeds the limits of the narrow terminal solid-solution boundary, and closely approaches the peri-tectic composition involving the brittle intermetal-lic compound, MoNi. Because of the peritectic reaction, fusion alloys are characteristically brittle, since the MoNi phase, being the last to form, tends to occur as a continuous grain-boundary network around each molybdenum grain. An added problem with this system is that the protective nickel-molybdate layer formed at high temperatures is unstable, undergoing one or more allotropic modifications upon cooling. The volume changes associated with this modification during cooling are such as to cause violent expulsion of the protective molybdate coating from the surface of the piece. This is, of course, quite detrimental in material exposed to cyclic temperature during service. The research reported here resulted from an attempt to overcome the aforementioned problems associated with the molybdenum-nickel alloys primarily by controlling the amount, size, and location of the MoNi phase. By using powder-metallurgy techniques of alloy preparation and sintering the blended molybdenum-nickel powder mixtures at a temperature below the peritectic reaction temperature, molybdenum-nickel alloys with a randomly dispersed MoNi phase were produced. MATERIALS The molybdenum powder used in the preparation of alloys for this study was commercial hydrogen reduced, minus 325-mesh (Tyler) material. Master alloys, by which nickel was added, consisted of elemental carbonyl nickel powder (12 average particle size), an alloy of 50 wt pct Ni-50 wt pct Cr, and compounds of MoNi, Ni,Si, and Ni2B. The nickel-chromium powder was prepared by filing a vacuum-arc-melted ingot, separating impurities magnetically, and screening to minus 200-mesh. The MoNi powder was prepared by pulverizing a hydrogen-sintered powder-metallurgy compact to minus 325-mesh material. Further sizing of this powder for study of effects of dispersion distribution was accomplished by air classification of the minus 325-mesh powder. The Ni2Si and Ni2B powders were prepared by crushing vacuum-sintered powder-metallurgy compacts to minus 200-mesh material. EXPERIMENTAL PROCEDURE Specimen Preparation—The general procedure followed in the preparation of alloys for testing is described as follows: 1) Blending. Either hand-blending of the powders in a ceramic mortar and pestle for X 1/2 or mechanical blending was used. Hand-blending seemed preferable for optimum homogeneity. 2) Compacting. Most of the blended powders were pressed to green compacts at pressures of 15 tons per sq in. in a single-action die, although some were pressed at 80 tons per sq in. A 1 X 11/4 X 1/4-in. green compact was the standard size for oxidation test material, and 7 X 1/2 X 1/4-in. compacts were used for fabricability test specimens. 3) Sintering. All green compacts were sinteredat

Jan 1, 1959