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By R. J. Colony

DEPOSITS of iron are widely scattered in the folded Cretaceous rocks and the associated igneous intrusives of Puerto Rico. Most of them are too small for commercial development, but a few have aroused some scientific and economic interest, among them the large body of residua] limonite at the west end of the island near Mayaguez1-6 (Fig. 1) and the mixed hematite and magnetite deposit on the southern slopes of the Sierra de Cayey, about four miles north of Arroyo.7-9 Neither of these orebodies has been developed, nor have investigations of the widely distributed deposits of magnetite, which include all the remaining occurrences of iron deserving of economic consideration, proceeded beyond the exploratory stage. With the possible exception of the mixed deposit near Arroyo, the magnetite is directly associated with andesitic and dioritic intrusives, which invade the Cretaceous rock section, and the bulk of it, occurring in calcareous sediments, is clearly of contact-replacement origin. The small deposit on Rio Portugues, north of Ponce, is found in a limestone band near its contact with an andesite dike.10,11 Two deposits of unde-

Jan 1, 1935

After a three-year period characterized by inflation, recession, depressed metal prices, lack of demand, enormous world inventories, and rapidly escalating costs, the Canadian mining industry is showing welcome signs of recovery. A rise in world metal prices and particularly strong demand for gold, uranium, and coal have stimulated the industry in early 1979. In this atmosphere of growing optimism, over 3000 mineral industry executives, economists, geologists, and mining and metallurgical engineers convened in Montreal, April 26-29, for Canada's largest mining convention, the Annual General Meeting of the Canadian Institute of Mining and Metallurgy.

Jan 6, 1979

By Henry Rawdon

THE following note describing the behavior of copper under rather unusual conditions is offered here for its suggestiveness rather than as a complete study of the question. The examinations described were made because of a request for information concerning the embrittlement of copper when heated in a molten salt bath (sodium chloride) for the purpose of cleaning it, as well as for softening it. It is well known that metals may be rendered very brittle by electrolytic action, in aqueous solutions, in all probability by the action of nascent hydrogen, and it was suspected that perhaps the embrittlement of the copper by means of the molten salt was produced in a somewhat similar manner. It was found that the copper was in contact with iron (or steel) while immersed in the molten salt, through the occasional use of an iron stirring rod, iron forceps for handling the pieces, and an iron pot for containing the fused salt. In the electrochemical potential series iron and copper stand some distance apart, copper being electronegative to the iron. Assuming that the two metals bear a similar relation to each other, when immersed in a bath of molten salt, as they do in an aqueous solution, they would be expected to form a galvanic couple, the copper being the cathode. By this means the copper might be embrittled, as often happens in aqueous solutions, by the action of the liberated hydrogen. In this case, however, the embrittlement must be attributed to some other agent than hydrogen. To demonstrate how copper may be embrittled under these conditions, two small rods, one of copper and the other of mild steel, approximately 3/8 in. (9.5 mm.) in diameter, were immersed in a bath of sodium chloride that had been heated somewhat above its fusion point (melting point of sodium chloride is 819° C.) and an electromotive force of approximately 6 volts from a storage battery was impressed upon the system. The copper was made the cathode and the action was continued for

Jan 2, 1920

By M. R. Pickus, I. W. Pickus

ORDINARILY age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type, Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a super-structure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,1 Janecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling, Similar changes have been observed in the binary gold-copper system,6 one alloy of which corresponding to the formula Cu3Au, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change, The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on 14-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. PRESENT INVESTIGATION As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By W. H. Yarroll Discussion by W. A. Griffith

W. A. Griffith (Head, Research Department, Phelps Dodge Corp., Morenci, Ariz.) - It is gratifying to see the increasingly common use of classical statistical procedures by metallurgical researchers. Mr. Yarroll has given excellent illustrations of the utility of multiple correlation analysis of complex metallurgical data. Our experience in applying these procedures to historical plant operating data has differed, however, from that which he suggests. The uninitiated frequently assume that the volumi-

Jan 1, 1969

By B. S. Gottfried

This paper is concerned with possible transport mechanisms which occur during segregated burning (i.e., burning in an oil reservoir in which the oil-bearing formation is overlain by a "clean" porous zone containing only gas). ,Two analytical models are presented. In the first, burning is assumed to occur at the gas-oil interface, and the dominant mechanism is taken to be the rate at which oxygen diffuses to the interface. The second model assumes that combustion occurs within the clean zone, with the dominant mechanism being the mechanism of fuel deposition from the oil-bearing formation to the clean zone. ,Comparison of the results of the analyses with limited experimental data indicates that the latter mechanism is much more plausible. Both models are idealized representations of the actual process and are somewhat conjectural, however, owing to the lack of more definitive laboratory or field data. INTRODUCTION In recent years there has been considerable theoretical and experimental research directed toward understanding the recovery of crude oil by underground combustion. Although two different recovery schemes have been proposed, known as forward and reverse combustion, it is only forward combustion that shows promise of becoming a practical recovery technique.17 Most of the analyses of the forward combustion process have considered it to be pistonlike; i.e., oil is displaced by a vertical combustion zone which, with its ensuing gases, pushes die oil forward as the flame front is propagated through the reservoir.l-8,ll,l2,14-16 However, information gained in field pilot studies indicates that, at least to a certain extent, forward combustion proceeds in a segregated manner in oil reservoirs.10 An ideal segregated system is one in which the oil-bearing formation is overlain by a "clean" porous zone containing only gas. The location of the combustion zone in such a system is not immediately evident, although combustion is believed to occur either at the gas-oil interface or within the clean zone. In either case, the combustion zone may be horizontal and it moves in parallel rather than in series with the produced oil. The purpose of this paper is to explore the likely mechanisms by which segregated burning can occur, and to determine the sensitivity of the resulting models to changes in various physical parameters. Two governing mechanisms are considered: the case of a horizontal combustion zone at the gas-oil interface with the rate of combustion governed by the rate at which oxygen diffuses to the interface, and the case of combustion within the clean zone with the combustion process controlled by the transport of fuel from the oil-bearing formation to the clean zone. Both models are somewhat hypothetical and involve considerable simplification of the actual process. However, the results allow some preliminary understanding of segregated burning which is useful in the absence of more definitive laboratory or field pilot data.

Jan 1, 1967

By R. P. Harvey, J. E. Walstrom, A. A. Brown

In view of the large number of wells directionally drilled from offshore platforms and urban drillsites, greater interest is being focused on the directional survey and on the uncertainty inherent in calculating the position of the bottom of the hole, or other benchmarks in the wellbore. Of the two methods presented here for evaluating this uncertainty, the first is analytical and uses the principles of probability and statistics. The second method uses Monte Carlo simulation to generate a pattern of the scatter of possible bottom-hole locations. Both methods are based on a model for which the usual assumption is made that the curvilinear axis of the wellbore is adequately represented by a large number, M, of linear segments joined end to end from the top to the bottom of the hole and closely following the course of the hole. The errors due to this approximation are assumed to be negligible and are not studied here. One form of the model is to consider that for a given hole there exists a perfect set of data describing it, of the above form. Each linear segment has an angle of inclination with the vertical 7, in radians, an azimuthal angle from true north xi in radians, and a length Si, in feet. The subscript variable, i, extends from 1 to M. Each of the M linear segments representing the axis of the wellbore has three components in the X, Y, and Z directions. These components are calculated from the equations: The bottom-hole coordinates as determined from the reference set of data for the wellbore are given by the following for i = 1 to M: X=SX, Y = Sy, Z=SZ; . (2) A directional survey instrument, lowered into the wellbore to the M segments, or stations, measures the values of the 7; and the 3,. In general, because of errors from various sources, the resulting angular measurements will not be precisely equal to the 7" and xi. Random variables l, and Ai are therefore considered with associated probability density functions fi(li) and gi(Ai), respectively, which represent the distributions of potential survey measurements for this hole. Since it is assumed that the values Si are accurately measured they are treated deterministically. The random variables corresponding to the surveyed bottom-hole coordinates are given, for i = 1 to M, by:

Jan 1, 1970

By John T. Norton

N order to attempt to arrive at a better under-Jl standing of the whole basic problem of sintering, these remarks will serve as an introduction for discussion that is included and will, perhaps, help to isolate specific questions which need to be answered or to suggest some definite avenues of investigation which should be followed. To bring some sort of logical order into the presentation, I will consider the various types of interaction between the metal to be sintered and the atmosphere which surrounds it, depending upon whether the phenomena are essentially chemical or physical in nature. For example, when the only necessary criterion for the satisfactory sintering of a certain powder is the removal of an oxide skin, then the problem of choosing a suitable atmosphere is primarily chemical; however, if a special surface condition as a consequence of the oxide skin removal is necessary for particularly effective sintering, then the problem becomes a physical one. Of course, the two aspects overlap considerably, but it may be possible to make a distinction in principle if not in practice. The chemical characteristics of the phenomena will be emphasized, since these are the better known. Metal-gas reactions involved in sintering are controlled primarily by the thermodynamics of the processes involved. In which direction will a reaction go and how far before it stops? The answer is to be found in the magnitude of the free energy change associated with the reaction. If a constituent is to be removed from the specimen as completely as possible or if a constituent is to be formed in the specimen as completely as possible, then one chooses conditions which are far from equilibrium so that the reaction is driven toward completion. On the other hand, if the composition is to be maintained at a desired value, then conditions are adjusted as closely as possible to the equilibrium point. This aspect of the problem is susceptible to quite precise analysis, provided, of course, that the significant reactions can be recognized and the required thermodynamic data are available. Conversely, if one asks how fast the reaction goes or how far it proceeds in a given time, the answer is frequently much more difficult to answer in quantitative terms. Yet the rate-con trolling factors of the reactions may be of primary importance in the success of a particular operation, especially where competing processes are at work. Both equilibrium and rate factors must be understood if a clear picture is to be obtained. For instance, in a process for carburizing titanium dioxide, is the difficulty of obtaining a stoichiometric Tic due to a true limitation of the equilibrium or simply to a very slow rate of reaction? An example of this appears in the work of Kalish and Mazza.' They showed that the oxygen content of sintered iron compacts was lower when sintered in pure hydrogen than in the case where the hydrogen was diluted with either argon or nitrogen. The equilibrium oxygen content of the iron would be the same in the two cases, since it is determined by the ratio of the partial pressures of water vapor and hydrogen and this pressure ratio is unchanged by dilution. The rate of oxygen removal, however, under the conditions of a constantly replaced furnace atmosphere, depends upon diffusion and thus upon the concentration of hydrogen in the furnace atmosphere. Possibly the clearest way to illustrate the interplay of these two factors is to consider in more detail some of the typical metal-gas reactions. Adsorbed Gases It is common experience that fine metal powders with their very large surface areas often contain large quantities of gas. This gas, which results from exposure to air or perhaps from some step in the

Jan 1, 1957

By Y. Oka, H. Majima

When a rock particle is subjected to an external force, internal stresses and deformations are experienced by the particle. Assuming that the breakage of a rock is mainly due to tensile stresses generated by the action of a pair of concentrated loads, F, directed in compression towards the loading points at the shortest distance, as illustrated in Fig. 1, the stress and deformation experienced by a particle of irregular shape can be determined with the aid of the theory of elasticity. According to the photoelastic experiments made by one of the present authors,' the stress states in a rock particle of irregular shape are quite similar to that of an inscribed sphere of diameter x, as indicated in Fig. 1, but accompanied by the faint stresses, in the vicinity of the particle outside of the inscribed sphere. Therefore, the stress components in an irregularly shaped particle can be estimated by referring to stress components in a sphere. Applying polar spherical coordinates to an elastic spherical body, as shown in Fig. 1, the stress components are all expressed as multiples of F /x2 and more or less influenced by the loading angle and Poisson's number m. In general, the energy w, acting on a rock particle is defined as the product of loading compression F

Jan 1, 1970

By L. F. Reinartz

ANOTHER year has rolled by. We are twelve months further away from the start of the depression and. therefore that much nearer to recovery. The accumulated needs and wants 'of our lame, virile population are ready to burst their bonds as soon as confidence returns and credit is stabilized. The steel industry has been harassed by uncertainty of the Government's attitude toward organized labor's de¬mands, and irregularity in volume of production. Steel labor, if left to its own devices, would in most instances, march shoulder to shoulder with the management of steel plants in their effort to pull the industry nut of the ?red.? Cooperation between management and men has improved considerably during; the year.

Jan 1, 1935

By V. Koump, T. F. Perzak, R. G. Olsson

Jan 1, 1965

By E. J. Dulis, A. Kasak, R. C. Westgren

The potential of uirought tungsten- and tantaluw-rich alloys of the W-Ta-Mo-Cb system was investigated for high-strength structural applications above 2500° F. Appreciable strengthening of tung-sten and tantalum—essentially attributable to solid-solzction effects—was obtained with binary, ternary, and quaternary alloys. Tensile strengths as high as 67,000 psi were achieved at 3000 OF. ThE quest for wrought structural materials which possess good strength properties at temperatures above 2000°F has led to a considerable research effort during the past decade. In addition to exploring the potential of various high-melting-point refractory metals (such as molybdenum, columbium, tantalum, and tungsten) for very high-temperature structural applications, alloy-development programs have been undertaken to achieve greater strengths than could be achieved with unalloyed refractory metals. The methods of strengthening refractory metal alloys have included both solid-solution and dispersion strengthening. General relationships among the relevant properties (melting point, recrystallization temperature, and high-temperature strength) of refractory metals indicate that the highest strengths at temperatures of 2500°F or higher would be obtained with tungsten-or tantalum-base alloys. Therefore, the present investigation was undertaken to determine the high-temperature strength potential of solid-solution strengthened alloys based on the binary system W-Ta; to effect further strengthening, minor additions of molybdenum and columbium (at the 6 and 12 pct levels) were made. The portion of the W-Ta-Mo-Cb quaternary alloy system of interest is shown schematically in Fig. 1. The component metals—W, Ta, Mo, and Cb—have a bcc structure at all temperatures, and their binary systems are mutually completely soluble.' Complete solid solubility in the W-Ta-Mo and W-Ta-Cb alloy systems has been demonstrated,' and, therefore, it was expected that the quarternary alloys of the system would also exhibit complete solid solubility at all temperatures. In the virtual absence of contamination by interstitial elements, all the alloys would be truly solid-solution strengthened. Twenty specific compositions of this investigation included binary, ternary, and quaternary alloys of the W-Ta-Mo-Cb system as well as unalloyed tungsten and tantalum. The compositions are shown in Table I. EXPERIMENTAL PROCEDURE Consumable-electrode vacuum-arc melting with ac power was used to produce small laboratory-sized, cylindrically shaped ingots (1-1/4 in. in diameter and 2 to 3-1/2 in. long) of the twenty compositions. A furnace was specially constructed to melt as many as four electrode rods simultaneously into molds lined with tungsten or tantalum sheet. High-purity rods of tungsten, tantalum, molybdenum, and columbium were used for consumable electrodes; the diameter of each rod was determined by the desired weight percentage of the component metal in a given alloy. The details of the construction and operation of the melting furnace will be discussed in another p~blication.

Jan 1, 1964

By B. C. Craft

Oil and gas development in Mississippi during the year 1933 was rather active and a number of important wildcat wells were drilled throughout the state. Mississippi showed an increase in drilling operations during 1933. There were 58 completions from 22 counties during this period, compared with 53 completions in 10 counties during 1932. The Jackson gas field in Hinds and Rankin counties continued to be the most active area with 26 completions, resulting in 17 gas wells, 2 oil wells, and 7 dry holes, compared with 38 gas wells, 1 oil well and 5 dry holes during 1932. A further attempt to extend the producing limits of the Amory gas field resulted in a dry hole. Extensive exploration in south Mississippi has proved the existence of ample source beds and presence of an extensive sandbody near the top of Cockfield. Core tests, supplemented by extensive geophysical work, have been carried on in Jackson, George, Harrison, Pearl River and Stone counties. Exploration will be continued in 1934. The most important deep test drilled in 1933, and the deepest well ever drilled in a southeastern state, was the Eastman Gardner et al., Bank of Seminary No. 1, sec. 26-8N.-15W., Covington County. This well went through about 1300 ft. of Selma chalk, and was abandoned in the Eutaw at 8004 ft. Another interesting operation during the past year was the Foster Creek Oil Corporation's Foster Creek Lumber Co. No. 1, sec. 14-2N.-2W., in the "Eastern Conroe Trend." This test is shut down at 3687 ft. in the Catahoula sandstone and has not encountered any important shows of oil or gas. A total of 107 of the 117 gas wells completed in the Jackson gas field since its discovery in 1930 are still producing, and have a combined open flow of approximately 3,724,896,000 cu. ft. It is reasonable to assume that this area will be rather inactive during 1934 as the maximum daily production during 1933 was 3,476,000 cu. ft. The 10 wells that have gone dead were edge wells. The water level is now between the sub-sea depths of 2190 and 2195 ft. The Gulf Refining Company's Rainey No. 1, sec. 13-5N.-lE., one of the early wells in the field, had gas and water at —2225 ft. That the field is under hydraulic control is

Jan 1, 1934

By A. A. Stripling

The Cretaceous limestone wells of the Mara/Maru-caibo Dist. of Venezuela are extremely prolific producers. To maintain production on cessation of natural flow, large scale gas-lift operations were commenced involving high production rates on caring Flow. For the design of these gas-lift installations it was essential to have some knowledge of the pressure gradients involved in casing flow, so that the required injection pressures, optimum gas injection raws, etc., could be forecast. This paper presents a method of calculating these annular pressure gradients. Basically the method makes use of an energy balance equation coupled with an empirical energy loss factor derived from field data. The calculations have been put in a form suitable for "punch card-type" calculating machines. A set of gradient curves for Mara/Maracaibo conditions covering flow rates up to 12,000 B/D, and GOR's of 500 to 2,000 cu fd/bbl is presented. From these curves the flowing BHP can be predicted from surface data and the vertical pow performance under varying conditions of gas injection can be estimated. The method has been applied to La Paz and Mam gas-lift operations for over three years and has given consistently accurate results. INTRODUCTION The Cretaceous limestone fields of the Mara/Maracaibo area in Venezuela are characterized by the presence of widely distributed fissure systems. Under these conditions individual wells frequently have extremely high potentials and such wells are generally flowed on the casing-tubing annulus in order to reduce the pressure loss in vertical flow. To maintain production on cessation of natural flow, an extensive gas-lift system was planned. As a first approach to this gas-lift design problem, an attempt was made to construct a set of empirical flowing gradient curves from the available subsurface pressure data. Such a method has been used successfully for tubing-flow conditions in California by Gilbert'. Unfortunately, the empirical construction of casing-flow gradient curves presents additional difficulties, as pres- sure bombs cannot bc run in the casing-tubing annulus against high rates of flow. Thus, the Full flowing gradients cannot be defined by actual measurement and the best that can be done is to obtain spot pressures at the tubing shoe. Under these conditions a vast accumulation of BHP data is required to construct a set of gradients. To the La Paz and Mara fields the majority of the available flowing pressure measurements fall into a relatively narrow GOR range, in the neighborhood of the solution ratio. While there appeared to be reasonable prospects of constructing gradient curves for this limited range, measurements at higher GOR's, which were of major interest for gas-lift operations, were relatively few and the prospects of constructing empirical curves cor~spondingly remote. As an alternative approach, the possibilities of a mathematical analysis of vertical flow conditions were investigated. May and Laird2fV n 1934 presented an excellent analysis of the vertical-flow conditions in the Anglo-Iranian Oil Co.'s fields. Their analysis was based on an energy-balance equation and calculated the losses due to kinetic energy, friction and slippage separately. By combining these losses with the total calculated available energy, the required depth-pressure traverse could be deduced. On applying the method to La Paz conditions, good results were obtained for tubing flow at high tubing-head pressures. However, for lower wellhead pressures (300 psi and under) the discrepancy between calculated and measured values increased appreciably. It was considered that this was probably due to energy losses caused by slippage or liquid hang-up in a continuous gas phase, for which it was difficult to visualize any analytical approach. In 1952 Poettmann and Carpenter4 presented a method of pressure gradient calculation which, while based on an energy-balance equation similar to that employed by May and Laird, made no attempt to evaluate the various components making up the total energy loss resulting from irreversibilities of flowing fluids. Instead, they proposed a method of analysis which assumed that all significant losses for multiphase flow could be correlated in a form similar to that of the Fanning equation for frictional losses in single-phase flow. They then derived an empirical relationship linking measurable field data with a factor which, when applied to the standard form of the Fanning equation, would enable the energy losses to be determined. The total available

By C. C. Harris, A. Jowett, S. K. Ghosh

An equation derived from first-order kinetics and accounting for return from froth to pulp has correlated continuous flotation data. The concentration of floatable material in the pulp can be altered either by changing the feed concentration or the feed rate. The latter does not affect the flotation rate constant, the froth to pulp return constant, and the concentration of non-floatable material in both the pulp and concentrate. Both the return constant and the concentration of non-floatable material in the pulp are directly proportional to the feed concentration, while the concentration of non-floatable material in the concentrate is related to the feed concentration. The investigation of the froth flotation process by continuous test methods, previously used by Brown and smith,1 Jowett and Safvi2 and Jowett and West,3 is being continued. Recent tests, primarily concerned with flotation cell design, have yielded kinetic data suitable for testing an equation proposed by Arbiter and Harris4 which postulates that a flotation process is defined by two rate constants: 1) the rate constant for mass transfer from pulp to froth. Previous workers have regarded this as the flotation rate constant. 2) the rate constant for mass transfer from froth to pulp, which has previously been ignored. THEORY Under continuous flow conditions at the steady state in Fig. 1 the equation developed4 is Symbols are defined in Table I. The air-liquid ratio terms4 have been omitted, since they are substantially constant for a given set of conditions. Also, for a system operating at the steady state Vf and V, remain constant and Eq. 1 can be written: Cp/Cc=b'/a,+Qc/a' [2]

Jan 1, 1963

By H. J. Gerritsen

From presently available components a portable, rugged, reliable apparatus can be built which will be able to detect methane concentrations of 0.1% and lower in air. Sensitivity and design considerations of the apparatus are given. Ways to build even simpler and cheaper apparatus in the future are indicated. Traditionally the problem of detecting and monitoring the presence of dangerous gases present in small concentrations in air has been a difficult one. Whether canaries,' or sophisticated chemical or thermal conductivity methods are used, they seem to be either slow, cumbersome, or otherwise not completely satis factory. A seemingly natural way of gas detection is to measure the strength of absorption undergone by light of a wavelength that the gas to be detected absorbs. This method has been difficult to apply in view of the low power output over a narrow wavelength range in the infrared from traditional glow bar light sources. Besides, the apparatus to select such a narrow band of wavelengths is quite costly and complex. The use of a laser solves these problems simultaneously. Although a variety of lasers are available to detect a variety of gases (such as carbon monoxide or methane) whose early detection would be desirable, this paper deals exclusively with the use of lasers for methane detection. ABSORPTION SPECTRUM OF METHANE IN AIR The absorption spectrum of pure methane is very well known.2-4 There are four fundamental vibrations, all occurring in the infrared of which only two absorb strongly. They occur at 3.3 µ and 7.7 µ. The absorption spectrum is quite complicated due to the fact that the methane molecule can rotate in a variety of rotational quantum states. These rotational states are furthermore split by anharmonic forces such as the Coriolis force.4 When methane is present in air at atmospheric pressure, much of the very fine structure due to the anharmonic force is washed out since the pressure broadening is of the same magnitude as the splitting due to anharmonicity. For most of the spectrum at 3.3 µ, the rotational lines are typically separated by 0.01µ while the individual linewidth is 0.0001 µ. It is thus very important that the laser emit at a wavelength that coincides with one of these rotational lines. Before elaborating on the point that such a laser exists and how it performs, it is necessary for later discussion to point out that in the

Jan 1, 1967

By D. S. Pye, J. P. Gallus

Successful hydraulic pressure treatment of oil and gas wells that have long producing intervals, multiple pay zones, fluid thief zones, or natural or induced fractures has long been a serious problem plaguing the petroleum industry. High fluid-injection rates, straddle packers, ball sealers, and either liquid or solid additives to the treating fluids are being used to cope with this difficult and costly problem.l-6 The use of ball sealers and straddle packers is limited, in practice, to wells that have been completed with perforated cemented casings or liners. Well stimulation with ball sealers and straddle packers is usually successful as long as the cement remains competent. The other techniques of diverting are used with all types of completions. However, there are two significant disadvantages of the high rate method: excessive horsepower requirements, and the need of large treating-fluid volume. Consequently, most well stimulation techniques that involve diverting depend upon ball sealers or granular materials. Liquid diverting agents, and some of the solid ones in use today, frequently will cause formation damage. On the other hand, the most popular particulate diverting agents often are so soluble in the treating fluid that they become largely ineffective; their particle size is severely reduced as they dissolve while being transported through thousands of feet of pipe to the formation face down hole. In our attempts to deal with the shortcomings of these diverting agents, we experimented with a large variety of potentially suitable deformable materials the solubility of which could be controlled. Following are the criteria for the diverting agent sought: 1. The material must be effective in reducing fluid loss to thief zones, including existing fractures and very high permeability layers in the formation to be pressure treated. 2. The material must have enough strength to bridge under the treating pressure. 3. The material must be insoluble or slowly soluble in the treating fluids so that the particles retain sufficient size to be effective after they reach the formation face. 4. The material must be completely soluble in the produced oil or condensate liquid so that it can be removed readily; it must not cause formation damage. A number of products consisting of various polymers blended with waxes and other solid hydrocarbons were examined. All these materials satisfied the criteria for a diverting agent and also exhibited some degree of plastic deformability. On the basis of initial tests of strength and hardness, several blends of wax and polymer were selected for extensive testing in the laboratory and the field. These compounds have congealing temperatures ranging from 140 to 190F; they are insoluble in water and soluble in oil. They conformed, therefore, to the criteria specified for a theoretically superior diverting agent. Laboratory and field tests were conducted using these wax-polymer materials to demonstrate that the use of a deformable diverting agent can significantly improve fluid diverting performance. Data in this

Jan 1, 1970

By R. W. Armstrong, D. H. Feisel

Self-diffusion in pure crystalline solids has been described through extension of the Cohen and Tum-hull volume -fluctuation model originally proposed for diffusion in simple liquids. It is shown, for a number of crystalline solids, that the self-diffusion coefficient, D, obeys the relationship where a is the lattice spacing, v the Debye frequency, Z' the lattice-volume fluctuation per atom required for a diffusion jump, and (?V/Vo) the relative increase in the lattice volume resulting from thermal expansion between O°K and the temperature under consideration. The calculated value of Z' is dependent upon the difiusion mechanism and the lattice geometry. ThE need for an increased understanding of mass-transport processes in crystalline solids has resulted in much research to determine rates of self-diffusion.' For several metals (e.g., copper, silver, and iron), the experimental values of the self-diffusion coefficient, D, have been determined over a large interval of temperature and the accuracy of D has been investigated through repeated experiments. Also, a number of empirical and theoretical diffusion studies have established a rational basis for understanding the D values for the different elements.2"6 The empirical diffusion analysis by Sherby and simnad6 supplied the main stimulus for the present study. Sherby and Simnad, reviewing the self-diffusion data for a substantial number of pure crystalline solids, suggested that sufficient data were available to establish with some certainty the apparent intrinsic material properties which influence D. Without explicit regard for any mechanism of diffusion, these investigators obtained an empirical relationship for D which correlated the self- diffusion coefficient for each element with the melting temperature, crystal structure, and valence of the particular element. Their analysis is only unsatisfactory in that the effect on D of crystal structure is not very clear and the valence to be assigned to an element is not always straightforward. The present study is an attempt, from a very different viewpoint from that of Sherby and Simnad, to establish a basis for understanding the self-diffusion coefficients for crystalline solids. This analysis was undertaken for the purpose of developing a general expression for D which would explicitly depend on the mechanism of diffusion. The main result of the study is that diffusion in crystalline solids may be described in terms of a volume-fluctuation model which was originally proposed by Cohen and Turnbull7 to describe diffusion in simple liquids. The model appears to be useful for predicting self-diffusion coefficients in crystals. The following sections describe the volume-fluctuation model for diffusion, the application of this model to crystals, and the resultant agreement with experimental data. 1) THE VOLUME-FLUCTUATION MODEL FOR DIFFUSION Cohen and Turnbull7'8 developed their model for liquid self-diffusivity for the purpose of describing certain properties of liquids, glasses, and the liquid-glass transition. A hard-sphere model for the liquid structure is used. In this model, the size of a spherical molecule or atom is fixed for all temperatures by the interatomic spacing at the absolute zero of temperature. At any temperature above O°K, the atom is viewed as being contained within a larger spherical cage defined by the interatomic spacing of the atoms at that temperature. A random distribution of varying cage sizes is assumed to exist in the liquid. An individual diffusion jump occurs when the free volume of an atom (the volume of the cage containing the atom minus the volume of the atom) is large enough for the atom to jump out of its cage. With this physical picture of diffusion in liquids, Cohen and Turnbull derive the following equation for self-diffusivity: D=Doe-yv*/vf [1] where Do is the product of three factors which are the diffusion-path geometry, the diffusion-jump distance, and the velocity of the diffusing atom, v*

Jan 1, 1964

By C. F. Cornell, R. C. Emmett, D. A. Dahlstrom

FOR many years the disk-type and cloth-covered drum filters have found widest application in liquid-solids separation, which uses continuous filters. The disk type is less expensive, occupies less floor space per square foot of filtration area, and requires negligible down time for filter media changing. However, because filter cloth is billowed out by the blowback in the cake discharge, it is very short-lived if the scraper blades are set too close. Consequently cake weight is very important in assisting cake discharge, which normally necessitates a minimum cake thickness of 3/8 to ½ in. Also, the vertical position of the disks eliminates the possibility of efficient cake washing for removal of soluble values. The disk-type filter is generally limited, therefore, to applications that require no cake washing and form relatively thick cakes within the normal range of filter cycle times. The conventional cloth-covered drum filter is a more flexible unit, permitting wider variation in the percentage of cycle time devoted to cake formation, dewatering, or washing, as required by the application. Thinner filter cakes can be discharged because a horizontal line across the filter medium at the location of the scraper blade is equidistant from the edge of the blade at all points. The scraper blade therefore may be set a short distance from the filter medium or, where wire winding is not used, a floating scraper can be utilized so that the contour of the cloth can be followed. The drum filter is generally employed when there are difficult filtering slurries with resultant thin cakes or when cake washing to recover soluble values must be practiced. Difficulties sometimes encountered in continuous filter operation can be summarized in the following four categories: 1) Low filtration and/or washing rates due to blinding of the filter medium. 2) Poor cake discharge resulting from sticky cakes, filter medium blinding, or too thin a cake for the particular type of filter. 3) High filter media costs caused by short life and frequent down times for cloth changing. This results from blinding or from abrasion by the scraper blade when cakes are thin. 4) Blowback of filtrate at cake discharge because not enough air passes through the cake to purge the drainage area and filtrate lines during dewatering. To reduce or eliminate blinding tendencies several modifications have been tried, for example, cover-cleaning showers, blowback under the feed slurry, and snap-blow cake discharge. In many cases, however, this simply retards the rate of blinding, since the filter medium is kept clean at its outer surface only by these methods. As blinding usually occurs within or on the back of the medium, the operator is finally forced either to remove the cloth and scrub the medium intensively with a cleaning solution or acid-rinse it on the filter—all resulting in down time, short cloth life, and additional costs.

Jan 1, 1959

By G. T. Engel, W. G. Gruzensky

Jan 1, 1960