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By Walter Renton Ingalls

Metallurgical literature has no record of any ore beneficiated for cadmium alone, and the cadmium of commerce is derived from zinc ore, with which cadmium is generally associated. Zinc ores free from cadmium—e.g., the ores of the Franklin and Stirling mines, New Jersey, and of Broken Hill in Rhodesia—are rare. Blende concentrates of 50 to 60 per cent grade have contained (in production of important tonnage) as much as I per cent Cd, which is unusually high. The concentrates from the Tri-State district average from 0.3 to 0.4 per cent Cd, which is high. The concentrates from mines west of the Rocky Mountains seldom are higher than 0.2 per cent. In the periodic system of the elements, cadmium is in the same group with zinc. Its properties and compounds are similar. Its metallurgy is also similar. Cadmium has a melting point of 320°C. and a boiling point of 778"C., while the melting point of zinc is 415'C. and the boiling point gos°C. These conditions, together with the lower reduction temperature of cadmium oxide, indicate means for. separating cadmium from zinc. Cadmium in spelter is viewed, if not as an impurity, at least as an alloying element that may be objectionable, its special effect being hardening. However, for some purposes, a little cadmium in spelter is desired, and 0.4 per cent may be permissible, even in spelter for rolling. Cadmium in spelter for brassmaking is completely volatilized at the temperature of that process, and in bygone days an immense quantity of cadmium must have been lost in the fumes from these furnaces. Pyrometalltjrgy—Early Cadmium compounds, sulphide and oxide, being more volatile than the corresponding compounds of zinc, loss of cadmium begins to occur from the first furnace operation. In normal roasting, even with Tri-State ore, this loss may not be very high. Raw ore, assaying 0.4 per cent Cd, may be expected to give a roasted product of the same assay, which would imply a cadmium loss of about 15 per cent. Roasted ore, assaying 0.4 per cent Cd when distilled at ordinary furnace temperature, yielded spelter containing about half of that in the ore charged. The first draw of spelter under these conditions may assay 0.8 per cent Cd (accounting for 22 per cent of the cadmium recovery) and after the several draws of spelter have been equalized the cadmium content may average 0.35 per cent. If, therefore, 2000 lb. of blende averaging 0.35 to 0.4 per cent Cd is roasted and distilled, there may be obtained 1000 lb. of spelter, assaying 0.35 per cent Cd or 3.5 lb. content, which entering into Prime Western spelter will be sold at the spelter price. It will be observed from the outline hereinbefore (summarizing conditions prior to the introduction of sintering) that the main loss of cadmium occurred in the distillation process and by failure to condense, which could be ameliorated by attaching a prolong to the condenser, thus collecting

Jan 1, 1944

By John E. Sherborne, William M. Newton

THE relation between the properties of electric logs and the fluid used in drilling a well is briefly discussed in this paper, and the fact that the resistivity of the drilling mud and its filtrate can appreciably affect such logs is shown. Apparatus was designed and a procedure established to determine the effect of various factors on the resistivity of drilling mud. Five muds commonly employed in California were tested and the following observations were made: I. The effect of raising the temperature from 80°F. to 180°F. is to decrease the resistivity of the mud or filtrate approximately 50 per cent. 2. The resistivity of the mud in most cases closely approximates that of its filtrate. 3. The change in the resistivities of muds caused by the addition of chemical is not the same function of the amount of chemical added for each mud. 4. The effect produced by increased sodium chloride content is to reduce markedly the resistivity of the mud and its filtrate. 5. Weighting materials, such as Baroid and limestone, tend to increase the resistivity of drilling mud. 6. Cement and counteracting reagents reduce mud resistivity.

Jan 1, 1942

By R. F. Mehl, R. F. Bunshah

A fast amplifier technique has been developed for the measurement of the rate of propagation of martensite in an Fe-29.5 pct Ni alloy. The time of formation of one plate of martensite is 3x10 sec and the rate of propagation is 3300 ft per sec approximately. IT has been known for some time that the plate-like structural unit of martensite forms from austenite with great rapidity. Wiester1 and Hane-mann, Hofmann, and Wiester took motion-pictures of the transformation as it occurs in a 1.65 pct C steel; they demonstrated that a single plate formed fully in the time interval between successive frames, viz., 1/20 sec, thus setting an upper limit. Forster and Scheil,3 using an Fe-Ni alloy with 29 pct Ni, recorded the sonic characteristics of the process electrically, upon an oscillograph, setting the upper time limit at 0.002 sec. Forster and Scheil,~ measuring the change in electrical resistance in the same alloy upon a cardiograph, set a limit of 0.02 sec. Forster and Scheil5 later, employing the same alloy, improved their technique, reporting an upper limit of 7.10 sec. In studying signals of such short duration, it is an important question whether the frequency response of the electrical system used is high enough compared to frequency of the pulse measured, or, put differently, whether the system is able to reproduce without distortion the signal arising, in this case, from the formation of a single martensite plate. Forster and Scheil (referring only to their last paper) obtained signals of a frequency of 30 kilocycles (hereinafter kc); this was about the frequency response of the equipment used; thus, if the signal had a frequency higher than 30 kc, it would still appear as a signal of frequency 30 kc. All of these results thus provided upper limits only. Recent developments in electronics have made available equipment with very high frequency response, very high sweep-speeds, high gain, etc. The electrical characteristics of such equipment, used in the present study, are given in Table I. Such equipment offers obvious attraction in the study of the rate of propagation of a martensite structural unit—and perhaps of other structural alterations proceeding at a very high rate. This paper reports an attempt to develop a technique employing such equipment to measure the time of propagation of a martensite structural unit and the variation of this with temperature, with the mode of formation—athermal and isothermal—in both polycrystalline and single-crystal samples; and from such measurements to obtain the rate of propagation. As will be seen, the results obtained are useful theoretically. Materials All data presented here are for an Fe-Ni alloy of the following analysis: 29.5 pct Ni, 0.027 pct C, 0.135 pct Mn, 0.094 pct Si, balance Fe. There were several reasons for choosing this alloy: 1—it is substantially the one used by previous investigators; 2—it exhibits both the athermala and the isothermal' mode of formation of martensite, both studied in detail by Machlin and Cohen; 3—the subzero temperatures of transformation in this alloy are experimentally very convenient; 4—it exhibits the "burst phenomenon";" 5—the change in electrical resistance upon the formation of martensite, a decrease, is great, approximately 50 pct.' The polycrystalline specimens were in the form of wires of 0.025 in. diameter; the single crystals were 1x1/4x1/4 in. Experimental Methods Electrical Apparatus: Fig. 1 is a schematic drawing of the electrical circuit used. The principle used in these measurements is the same as that used by Forster and Scheil." A small direct current, about 1 to 2 amp, is passed through the sample. When a martensite plate forms, the resistance of the sample changes and a high frequency signal is generated. This signal is picked up by the probes attached to the sample, fed into the bank of amplifiers and thence to the vertical deflection plates of a cathode-ray oscilloscope. The signal itself triggers the oscilloscope trace which flashes across the tube face and is photographed by means of a 35 mm movie camera at the end of a light-tight hood. The camera has no shutter. As soon as the signal flashes

Jan 1, 1954

I would like to congratulate the authors on an interesting paper and, in particular, on their justification of the use of superposition in treating gas wells. They state, however, that no theory has previously been developed lor treating the variable rate drawdown case. In a paper published a few years ago by my colleagues and myself, a method is described which allows a constant rate drawdown curve to be derived for any well. regardless of real rate variations. This method has the great advantage that it is not necessary to make any assumptions regarding the form or uniformity of the reservoir, and the derivation suggested by the present authors is simply an idealized case of our more general treatment. In the light of several years' experience in the derivation of constant rate drawdown curves: I would like to point out that the method proposed by Odeh and Jones may lead to confusing answers, particularly if applied over an appreciable time interval. The reason is that, if pressures are measured when a well is flowing, non-linearities in plots like Figs. 1 and 2 can arise due to either (1) changes in the skin factor with time and/or flow rate, or (2) an inhomogeneous reservoir. Separation of these two effects is only possible if some of the pressures used in the analysis are measured when the well flow rate is 0 or, in other words. during brief shut-in periods. REFERENCES 1. Arthur, K. B.. Metunomski, Z. G. and Ruche, Ms "Intetet ct methode d'utilisa tion des mesures de pression [)our Petude des gisemonts" Revue de T'I.F.P. (Nov., 1962) XVII, 1299. 2. Thomere, R. and Arthur, K. R.: "Analysis of the Pressure Bet~avior of a Production Well Subject to Interterence and Its Application to Reservoir Models", Paper SPE 1189 presented at SPE :Amund Fall Mecting Ireld in Denwer, Colo. (Oct. 3-6, 1965).

Jan 1, 1966

By Frederic Benard

The treatment of Balbach-Thum slimes at Copper Cliff by the Ontario Refining Co, is of interest because it differs considerably from methods usually employed for the recovery of fine gold from parting-plant slimes. Owing to the comparatively high percentages of palladium and platinum, wet methods are used to remover the greater proportion of these metals before electrolytic refining in the Wohlwill cells. The Plant The platinum-metals department, Wohlwill room, and gold-melting room extend along the north side of the silver refinery and are separated from the parting plant by a glass partition (Figs. 1 and 2). The platinum-metals department resembles a laboratory built on a large scale, with the various pieces of equipment laid out on terraces to facilitate handling. Because of the corrosive nature of the solutions, chemical stoneware is used throughout. Elevation of acids is accomplished by means of Mariotte bottles. On the top level are three steam-jacketed stoneware kettles of 50-gal. capacity, also a packed tower. One kettle is used for digesting the slimes while the remaining kettles are used for precipitating the gold. The dissolver is equippcd with a treated concrete hood, which is connected to the flue system. Gases are drawn off through the packed tower by means of a 6-in. stoneware exhaust fan. A 15 per cent solution of sodium carbonate is continually circulated through the tower. On the intermediate level are two suition filters, one for removing silver chloride and the other for the gold sand. The filter medium consists of an asbestos pad covered with a filter paper on which is a layer of twill. On the bottom level are two rectangular cementation tanks, 24 by 48 by 24 in. deep, and a suction filter used for removing the platinum-metal concentrates. The circulating pump for the packed tower is also here. Suction is provided by a vacuum pump having a capacity of 8 cu. ft. at 20-in. vacuum.

Jan 1, 1944

By Frederic Benard

THE treatment of Balbach-Thum slimes at Copper Cliff by the Ontario Refining Co, is of interest because it differs considerably from methods usually employed for the recovery of fine gold from parting-plant slimes. Owing to the comparatively high percentages of palladium and platinum, wet methods are used to remove the greater proportion of these metals before electrolytic refining in the Wohlwill cells. THE PLANT The platinum-metals department, Wohlwill room, and gold-melting room extend along the north side of the silver refinery and are separated from the parting plant by a glass partition (Figs. 1 and 2). The platinum-metals department resembles a laboratory built on a large scale, with the various pieces of equipment laid out on terraces to facilitate handling. . Because of the corrosive nature of the solutions, chemical stoneware is used throughout. Elevation of acids is accomplished by means of Mariotte bottles. On the top level are three steam-jacketed stoneware kettles of 50-gal. capacity, also a packed tower. One kettle is used for digesting the slimes while the remaining kettles are used for precipitating the gold. The dissolver is equipped with a treated concrete hood, which is connected to the flue system. Gases are drawn off through the packed tower by means of a 6-in. stoneware exhaust fan. A 15 per cent solution of sodium carbonate is continually circulated through the tower. On the intermediate level are two suction filters, one for removing silver chloride and the other for the gold sand. The filter medium consists of an asbestos pad covered with a filter paper on which is a layer of twill. On the bottom level are two rectangular cementation tanks, 24 by 48 by 24 in. deep, and a suction filter used for removing the platinum-metal concentrates. The circulating pump for the packed tower is also here. Suction is provided by a vacuum pump having a capacity of 8 cu. ft. at 20-in. vacuum.

Jan 1, 1938

By H. B. Charmbury, D. R. Mitchell

Recovery of fine coal from solids reporting to wash water has become increasingly important. These solids range from about 28 mesh to 0 and constitute 3 to 7 pct by weight of the feed tonnage to a coal preparation plant. In the past they were usually wasted to streams, but present clean stream legislation makes it necessary to remove them from the wash water and, if economically possible, recover the associated coal as a saleable product. Where these solids are not wasted to streams or to slime ponds they are recovered by thickeners and filters. Since filter cake is often high in ash or sulfur, or both, it is not readily marketed or used. Common practice is to mix it with other plant products, generally slack or cleaned run-of-mine. Uniform blending is difficult, not only because the impurity is usually high, but also because during certain operating periods it is possible to get a concentration of this filter cake in a railroad or barge. At some plants filter cake has been derived from the froth flotation clean-up of Dorr thickener underflow. The operating circuits required for a froth flotation plant make this a comparatively high-cost treatment, and in the last few years experiments have been carried out with bulk oil methods. These also are quite expensive and lend themselves only to special situations. Table I gives some characteristics of thickener underflows for plants in the Pittsburgh area treating Pittsburgh seam coal. It will be noted that there is a concentration of impurities in the -200 mesh sizes.

Jan 1, 1960

By B. Ramaswami, U. F. Kocks, B. Chalmers

This paper describes the tempetrature, solute (gold), and orientalion dependence of the plastic rleforlirnlion of silver single crystals. The virgin flow stress, To, and its temperatutre dependence incrense with increase in solute concentration. el decreases with decrease in temperature below room teiirperature and with increase in solute coucentralion. The dependence of 011 on temperature arid solute sontenl is due to the dependence of Ts on the two variables. An increase in ts, due to either the temperature or the solute conlent, results in a decrease of e11 in crystals of single-slip orientation and an increase of 011 in crystals of' (100) find (111) orientation. is orientation-dependent and at all the temperatures and in all the materials studied. The Leveling off of the engineering stress-strain curve in crystals of (100) 07-ientotion at a stress tl, is associated with extensive cross slib. The temperature and strain -rate dependence of tl are similar to those of indicating that a rate process is the cause 01 this phenomenon. The plastic deformation of silrer crystals of (110) orientation is multiple to that of crystals of single-slip orientation. THE work hardening of fcc crystals has been the subject of intensive investigations in the past 15 years. The effect of orientation, deformation temperature, solutes, second phase or precipitates, strain rate, etc., has been studied in a number of fcc metals.'-5 In spite of the considerable amount of work reported on the dependence of work hardening on the orientation, temperature, and solute concentration, certain aspects of the plastic deformation of fcc crystals have not been clarified. For instance, with the exception of a few investigations,6-8 where crystals of multiple-slip orientations have been studied, almost all the studies have been on crystals of single-slip orientations. Hence, a major portion of this study has been devoted to the dependence of plastic deformation on the multiplicity of slip systems and the enhanced possibility of dislocation interactions resulting from such multiplicity. Further, the abnormally low rate of work hardening observed at large strains at certain temperatures in crystals of the (100) orienta-tion 6-8has not been explained satisfactorily. It is the aim of this study to clarify this aspect of the orientation and temperature dependence of the plastic deformation of fcc single crystals. The work-hardening characteristics of single crystals of aluminum of ( 110) orientation have been studied at room temperatur "'12 and above." They have not been studied at temperatures where the virgin flow stress is dependent on temperature or where, in Seeger's terminology is important. The work hardening of single crystals of (110) orientation is of interest for another reason. As shown in Table I, the dislocation reactions that are possible in the (110) orientation are similar in certain respects to those that are possible in the (100) orientation. Hence, the deformation of single crystals of silver of (110) orientation was studied in the temperature range 100° to 900°K at intervals of 200°K. The effect of solute concentration on the plastic deformation of fcc single crystals of single-slip orientation has been studied by several investiaators.> In all of these investigations—with the exception of Ref. 20—single crystals of identical orientation have not been used, with the result that the orientation dependence of plastic deformation is superimposed on the effect of the solute. In addition, the effect of the solute on the work-hardening characteristics of single crystals of multiple-slip orientations has not been studied by the previous

Jan 1, 1965

By W. H. Burke

Deeper drilling, resulting in greater circulating distance and pressure, has directed attention to the advantages of the study of properties and control of rotary muds, which until recently have not had much consideration. One fundamental property of muds is viscosity, and viscosity is influenced by the quantity and character of colloidal material and can be controlled by chemical treatment. Colloidal Matter of Rotary Muds Two types of colloids are found in muds; the hydrophobic and the hydrophilic. Hydrophobic colloids do not associate intimately with water and are sensitive to small quantities of electrolytes. Hydrophilic colloids associate intimately with water, but are not so sensitive to electrolytes. The colloidal particles of rotary muds are derived from clay; In clay the particles may range in size from submicroscopic to macroscopic; a substance is a clay if the greater proportion of the particles are within the size limits prescribed for clay. The larger particles are inert and have no effect on the viscosity of normal hydrophobic colloidal muds. There are two theories accounting for the colloidal properties of clay-water suspensions: (1) the physical theory, that clay in water is a coarse colloidal suspension, and (2) Ashley's1 theory, that clay is a granular material with a colloidal gel surrounding the crystalline grains. The most important colloidal substances known to exist in clays besides the clay particles are: (1) colloidal silica, (2) colloidal alumina, (3) colloidal ferric hydroxide, (4) colloidal silicates, and (5) colloidal organic matter. Plasticity, a peculiar property of clay-water suspensions, is due to the colloidal particles. It is commonly (although not with strict accuracy) measured in terms of viscosity, and depends upon the amount and the state of flocculation of the colloidal matter present in the suspension. Fluidity in a rotary mud may be caused by a lack of colloidal clay particles or by deflocculated or flocculated clay particles, while viscosity in a

Jan 1, 1935

By Enrique Touceda

For a number of years prior to the world war, the firm of Geo. H. Thacher & Co., of Albany, N. Y., was engaged in the manufacture of marine and other gray-iron castings. At the outbreak of the war the firm decided to specialize in the manufacture of propeller wheels. It attacked the problem, therefore, from a foundry point of view, seeking to produce a casting that would be so accurate that no subsequent machining would be required on the blades, also from the point of view of the ship builder. There were two general methods of manufacture, the shortcomings of which have been freely acknowledged. In the sweep method, the nowel, or bottom half-mold, for each blade is swept up by a spindle beam and pitch race, while the top half-mold for each blade is built up individually. In the pattern method one individual blade, with the hub or hub portion, is mounted on a spindle and the individual blade mold formed, the pattern is then rotated on the spindle to the position for the next blade, etc. In rare cases wheels were made from a solid pattern. Owing to the cost of the pattern, its failure in many instances to be correctly made, and (when made of wood) its early and sure distortion the disadvantage of this pratctice is obvious, while metal patterns in most instances were prohibitive in cost. In these methods both green-sand and loam molding was practiced. The casting produced by either method can be considered only as a blank from which the propeller must be machined. The back surface of each blade must be chipped to the templet and through this procedure chipped to such accuracy as will be required for a static balance. Inasmuch as the work done by the machine tool is confined to the driving face of the blades, not only is perfection most difficult, but corrosion will be greater because of the removal of the dense skin of the casting and the local strains set up by the pneumatic tool in chipping. To produce a finished 9-ft. propeller for a Navy destroyer required from 8 to 21 days of foundry work and about the same length of time for the machining. Through the use of the Thacher process, only as many hours are required, besides it is possible to produce a finished casting in perfect conformity with any particular propeller-wheel design.

Jan 1, 1922

By Enrique Touceda

For a number of years prior to the world war, the firm of Geo. H. Thacher & Co., of Albany, N. Y., was engaged in the manufacture of marine and other gray-iron castings. At the outbreak of the war the firm decided to specialize in the manufacture of propeller wheels. It attacked the problem, therefore, from a foundry point of view, seeking to produce a casting that would be so accurate that no subsequent machining would be required on the blades, also from the point of view of the ship builder. There were two general methods of manufacture, the shortcomings of which have been freely acknowledged. In the sweep method, the nowel, or bottom half-mold, for each blade is swept up by a spindle beam and pitch race, while the top half-mold for each blade is built up individually. In the pattern method one individual blade, with the hub or hub portion, is mounted on a spindle and the individual blade mold formed, the pattern is then rotated on the spindle to the position for the next blade, etc. In rare cases wheels were made from a solid pattern. Owing to the cost of the pattern, its failure in many instances to be correctly made, and (when made of wood) its early and sure distortion the disadvantage of this pratctice is obvious, while metal patterns in most instances were prohibitive in cost. In these methods both green-sand and loam molding was practiced. The casting produced by either method can be considered only as a blank from which the propeller must be machined. The back surface of each blade must be chipped to the templet and through this procedure chipped to such accuracy as will be required for a static balance. Inasmuch as the work done by the machine tool is confined to the driving face of the blades, not only is perfection most difficult, but corrosion will be greater because of the removal of the dense skin of the casting and the local strains set up by the pneumatic tool in chipping. To produce a finished 9-ft. propeller for a Navy destroyer required from 8 to 21 days of foundry work and about the same length of time for the machining. Through the use of the Thacher process, only as many hours are required, besides it is possible to produce a finished casting in perfect conformity with any particular propeller-wheel design.

Jan 1, 1922

By Fred P. Dewey

Although coke is the acknowledged metallurgical fuel, and has been extensively used in this country for more than thirty years, yet the facts on record in regard to its physical properties are exceedingly meagre; and this is also true, but in a less degree, of its chemical composition. An investigation is being carried on in the National Museum which is intended to supply, so far as may be, this deficiency, and through the kindness of Professor Baird, Director of the Museum, I am permitted to present to the Institute a summary of a portion of the results already obtained. So far as I am aware, the credit for the first systematic investigation of the physical properties of coke belongs to Mr. John Fulton, Mining Engineer of Cambria Iron Co. The results of this investigation have been published in Report L, Second Geological Survey, Pennsylvania, 1875, and in a pamphlet setting forth the advantages of the Connellsville coke, the latter published also by the " Virginias"* His results are not altogether free from experimental errors, and the assumption that "the specific gravities of coke and water are very nearly alike "- is scarcely warranted. It has seemed to me, therefore, desirable to make an independent investigation of the physical properties of coke on a plan somewhat different from that adopted by Mr. Fulton. This is the investigation now being carried on at the National Museum.

Jan 1, 1884

By Henry D. Hibbard

The finishing and casting temperature of steel is a subject concerning which there is so much to learn that some temerity is required to write about it. This paper is, therefore, suggestive rather than dogmatic, though the views expressed seem now to the writer to be correct; nevertheless, they may be modified by future developments or discoveries but until then may be of some utility, particularly to beginners in the making of steel. Consideration is limited to the temperatures of simple steels, also called carbon steels, which are those in which carbon is the only element introduced for the purpose of conferring desired physical properties. Alloy steels will receive attention later. Three things largely determine what a batch of steel really will be; via., composition, casting temperature, and rate of teeming. Each has its advocates as being the most important; but they are so interrelated that each must conform to or be right for the other two. When one is claimed to be the most essential to have right, that, probably, was the one that it was found had to be of a certain description, within narrow limits, to suit the already adopted variations of the other two; that is, it was the last of the three to be brought into line. The term "casting temperature" is rather indefinite as there ale several temperatures to which the term may be applied. Most writers who have mentioned casting temperature of steel have alluded to it in relative terms. The few who have given actual temperatures, including Langmuir, Burgess, Styri, and Bash, do not give full information about them. Their results demonstrate the efficiency of pyrometers used rather than aid the steelmaker. In order to understand and use the temperatures, one should know in each case what the steel was, the stage at which the temperature was taken, whether it was usual or not, and whether or not it was right for that steel at that stage. When these

Jan 1, 1925

By J. U. Messenger

A technique is described whereby the resistance of an emudian to breaking can be quantitatively determined. Produced ailfield emulsions are usually the water-in-oil type and, accordingly, do not conduct an electrical current. However, there is a threshold of A-C voltage pressure above which an emulsion will break and current will flow. The more stable an emulsion, the higher the required voltage. A Fann Emulsion Tester, modified so that low voltages (0 to 10 v) can be accurately measured, is suitable. This technique has application in evaluating the effect of a demuksifier on the stability of an emulsion. Emulsions can, in essence, be titrated with demulsifiers by adding a quuntity of demulsifier, stirring, and measuring the voltage required to cause current to flow. Any synergistic effect of two or more materials added simultaneously can be followed accurately. A demulsifier that significantly lowers the threshold voltage (from 100 to 400 v to 0 to 10 v for the emulsions in this study) is effective and can cause the enlulsion to break. A demulsifier that will bring about this drop in the threshold voltage at low concentration ir very desirable. The technique is also well adapted for rapidly screening demulsifiers. INTRODUCTION Stable emulsions in produced reservoir fluids resulting from certain well stimulation and completion procedures are common problems. The use of suitable demulsifiers can often mitigate these difficulties. At the present time, a rapid and efficient method for selecting satisfactory demulsifiers is not available. It is badly needed. Reliance is now placed primarily on trial-and-error procedures. A new test method has been developed which permits a more rapid and precise selection of demulsifiers. It involves measuring the electrical stability potential of an emulsion before and after a demulsifier has been added. This paper describes this method and shows where it should have application in field emulsion problems. NATURE OF OILFIELD EMULSIONS Two immiscible components must be present for an emuhion to form; we are concerned here with crude oil and water. An emulsifier must be present for tin emulsion to be stable. J Emulsifiers can be substances which are soluble in oil and /or mter and which lower interfacial tension. They can be colloidal solids such as bentonite, carbon, graphite, or asphalt which collect at the interface and are preferentially wet by one of these phases. Unrefined crude oils can contain both types of emulsifiers, A popular theory is that, of the two phases in an emulsion, the dispersed phase will be the one contributing most to the interfacial tension.' Usually this phase contains the least amount of emulsifier. The stability of a water-in-oil emulsion is affected by the fol1owing: l) viscosity; (2) particle or droplet size; (3) interfacial tension between the phases; (4) phase-volume ratios; and (5) the difference in density between the phases. A stable emulsion is usually characterized by high-viscosity, small droplets, low interfacial tensions, small differences in density between its phases, and slow separatian of the phases. It also has low conductivity (high electrical stability potential). Water-in-oil and oil-in-water emulsions"' are both common; however, oil field emulsions are predominantly water-in-oil emulsions. The emulsions which commonly occur during oompletion and stimulation operations contain a combination of several of the following: acids, fracturing fluids (oil, water, acid), and formation water and oil. Produced emulsions usually contain formation water and oil. Emulsions form in oil wells because oil and water are mixed together at a high rate of shear in the presence of a naturally occurring or unavoidably produced emulsifier. During the completion and stimulation of productive zones, and while formation fluids are being produced, oil and water are very often commingled. These mixtures are formed into emulsions by agitation which occurs when the fluids are pumped from the surface into the matrix of the formation or produced through the formation to the surface. Restrictions to flow (such as perforations, pumps, and chokes)".'" increase the level of agitation; tight emulsions are more likely to form under these conditions. Often an emulsified droplet is an emulsion itself.'" Therefore, emulsion-breaking problems can be quite complex. The complexity can be even greater if a third phase (gas) is included. Demulsifiers operate by tending to reverse the form of the emulsion. During this process, droplets of water become bigger, viscosity is lowered, color becomes darker, separation of the phases faster and electrical stability potential approaches zero. Any of these effects could be followed as a means of determining emulsion stability. However, electrical stability potential is the most reproducible and most easily measured parameter for following the stability of a water-in-oil emulsion.

Jan 1, 1966

By A. G. H. Anderson, Eric R. Jette

A few years ago, while the writers worked on the constitution of ternary and quaternary alloys consisting mainly of iron, chromium and siliconl,2 some information on microstructures and hardness, not incorporated in the published work, alas obtained. It has not been possible to do any further work on the properties of the alloys. The information possessed is hereby presented for the interest it may have in connection with the constitution of the alloys. Microstructures Referring to the iron-chromium-silicon diagram,' the regions that received most attention were those in which the sigma phase appears. It was found that the mode of occurrence of this phase varied much with the condition under which it mas formed, and the mode influenced considerably the hardness of the alloys. In some slowly cooled alloys, well within the alpha + sigma-phase boundary, sigma occurs in pabterns suggesting a eutectic. The structure of such an alloy is shorn in Fig. 1, showing it to be partly coarsely laminated and partly globular mottled. In other annealed and slowly cooled alloys, the lanlinated structure is entirely absent, and sigma appears in an irregular distribution of sharply cornered elongated areas (Figs. 2 and 3). These areas all possess a more or less mottled structure. A carbide phase is also visible in these two photomicrographs; it is represented by bright white arras of various shapes, sometimes apparently enveloping the sigma. Quenched and aged specimens, whose compositions arc: located near the phase boundary between alpha and sigma + alpha regions, have structures not unlike martensite (Figs. 5 and 6). Fig. 4 shows the structurc of alloy No. 35 as quenched from 1100" C.; it is a typical solid solu-

Jan 1, 1938

By Eric R. Jette, A. G. H. Anderson

A few years ago, while the writers worked on the constitution of ternary and quaternary alloys consisting mainly of iron, chromium and siliconl,2 some information on microstructures and hardness, not incorporated in the published work, alas obtained. It has not been possible to do any further work on the properties of the alloys. The information possessed is hereby presented for the interest it may have in connection with the constitution of the alloys. Microstructures Referring to the iron-chromium-silicon diagram,' the regions that received most attention were those in which the sigma phase appears. It was found that the mode of occurrence of this phase varied much with the condition under which it mas formed, and the mode influenced considerably the hardness of the alloys. In some slowly cooled alloys, well within the alpha + sigma-phase boundary, sigma occurs in pabterns suggesting a eutectic. The structure of such an alloy is shorn in Fig. 1, showing it to be partly coarsely laminated and partly globular mottled. In other annealed and slowly cooled alloys, the lanlinated structure is entirely absent, and sigma appears in an irregular distribution of sharply cornered elongated areas (Figs. 2 and 3). These areas all possess a more or less mottled structure. A carbide phase is also visible in these two photomicrographs; it is represented by bright white arras of various shapes, sometimes apparently enveloping the sigma. Quenched and aged specimens, whose compositions arc: located near the phase boundary between alpha and sigma + alpha regions, have structures not unlike martensite (Figs. 5 and 6). Fig. 4 shows the structurc of alloy No. 35 as quenched from 1100" C.; it is a typical solid solu-

Jan 1, 1938

DURING the past year the Committee on Coal and Coke has been collecting data concerning various points in the bituminous industry about which a large amount of misinformation circulates through the press and, in some cases, through the coal trade papers. The data presented have been compiled by various members, from the most authentic sources available, and where possible cover the period 1913-1924. They will enable comparisons to be made within the industry, and of this and other industries, and will explain some of the differences between conditions existing now and in the prewar period. CAPACITY AND OVER-DEVELOPMENT The capacity of bituminous mines is frequently stated at figures ranging between 800,000,000 to 1,400,000,000 tons per year. Table 1 shows statistics for the industry, mainly from U. S. Geological Survey sources but partly from U. S. Coal Commission reports. Column 3 gives the mine capacity with equipment and labor as of given date, as estimated from the data published by the U. S. Geological Survey. This is calculated for each State by obtaining the total man days worked as. reported by the operators (multiplying average men employed by total days worked at each mine) and dividing this figure into the total production, getting the production per man day; this figure times number of men employed times 308 (a theoretical full working year) equals estimated- full-time capacity. Two major objections are made to this method-one that the total number of men employed is used, instead of the number actually working, and the other that the number of days used only deducts Sundays and five holidays. The first objection is answered by the fact that the same number of men is used in estimating capacity as is used in actual production, and while this number is always from 12 to 20 per cent. more than are actually working, this condition exists at all times, although it is worse at times of maximum output. Few coal men will agree with the conclusion that the use of 308 days is correct, as it is practically impossible to keep any mine working full time at the same

Jan 2, 1926

By T. S. West

Completion and production data presented for three wells in the Oakville area of Live Oak County, Texas, which were completed near the gas-oil or water-oil contact, indicate that coning may not be as prevalent a cause of failure in such cases as is commonly assumed. Failure in the cases discussed is indicated to be due instead to: (I) erosion of the formation, (2) flowing out of mud filter cake, or (3) failure of the cement. An open-hole gravel-pack type of completion procedure is proposed for preventing failures of this kind by preventing movement of all solid material in the space in which completion is made. Various combinations of layers of gravel, sand, and cement are utilized for this purpose. Experimental results and theoretical discussion as to the applicability of gravel pack completion are included. Introduction This paper is primarily a study of the reasons for failure of oil-well completions near the gas-oil or oil-water contact, and suggests a procedure for increasing the efficiency of this type of completion. The value of improvement in completion effectiveness near the gas or water zone is not confined, however, to wells of relatively thin oil columns. Thick oil columns become thin as depletion progresses. It would seem to follow that the minimum distance from the gas or water zone at which completion can be made in a new well indicates the limit to which depletion may be carried in a well having an oil column of any initial magnitude. Only four ways can be postulated in which high gas-oil or water-oil ratio can initially occur if the zone exposed for production is within the oil column: 1. Failure of the cementing material. 2. Vertical coning. 3. Failure along the boundary between the cement and the wall of the well. 4. Failure of the formation comprising the wall of the well. Cementing materials such as portland cement and plastics have reached a high stage of development. Failures of this type are probably due almost always to extraneous causes such as mud contamination rather than to faulty cementing material. Vertical coning can and obviously does occur. However, the usual occurrence of thin impermeable streaks in sand sections and the success with which open-hole drill-stem tests can be made near the gas-oil contact suggest that over-all effective vertical permeability, and in turn vertical coning, is less prevalent than frequently is assumed. Much has been written on failure by flowing out of the mud filter cake between cementing material and the formation. A filter cake is always present if, prior to cementing, mud has come in contact with a permeable formation at pressures exceeding the pressure head of the fluid it contains. Mechanical methods are in use for removing filter cake during the cementing operation? which undoubtedly are of

Jan 1, 1947

By T. S. West

Completion and production data presented for three wells in the Oakville area of Live Oak County, Texas, which were completed near the gas-oil or water-oil contact, indicate that coning may not be as prevalent a cause of failure in such cases as is commonly assumed. Failure in the cases discussed is indicated to be due instead to: (I) erosion of the formation, (2) flowing out of mud filter cake, or (3) failure of the cement. An open-hole gravel-pack type of completion procedure is proposed for preventing failures of this kind by preventing movement of all solid material in the space in which completion is made. Various combinations of layers of gravel, sand, and cement are utilized for this purpose. Experimental results and theoretical discussion as to the applicability of gravel pack completion are included. Introduction This paper is primarily a study of the reasons for failure of oil-well completions near the gas-oil or oil-water contact, and suggests a procedure for increasing the efficiency of this type of completion. The value of improvement in completion effectiveness near the gas or water zone is not confined, however, to wells of relatively thin oil columns. Thick oil columns become thin as depletion progresses. It would seem to follow that the minimum distance from the gas or water zone at which completion can be made in a new well indicates the limit to which depletion may be carried in a well having an oil column of any initial magnitude. Only four ways can be postulated in which high gas-oil or water-oil ratio can initially occur if the zone exposed for production is within the oil column: 1. Failure of the cementing material. 2. Vertical coning. 3. Failure along the boundary between the cement and the wall of the well. 4. Failure of the formation comprising the wall of the well. Cementing materials such as portland cement and plastics have reached a high stage of development. Failures of this type are probably due almost always to extraneous causes such as mud contamination rather than to faulty cementing material. Vertical coning can and obviously does occur. However, the usual occurrence of thin impermeable streaks in sand sections and the success with which open-hole drill-stem tests can be made near the gas-oil contact suggest that over-all effective vertical permeability, and in turn vertical coning, is less prevalent than frequently is assumed. Much has been written on failure by flowing out of the mud filter cake between cementing material and the formation. A filter cake is always present if, prior to cementing, mud has come in contact with a permeable formation at pressures exceeding the pressure head of the fluid it contains. Mechanical methods are in use for removing filter cake during the cementing operation? which undoubtedly are of

Jan 1, 1947

By W. B. Gogarty

The reported decreases in water mobility do not seem unusual in view of non-Newtonian fluid properties. Shear stress vs shear rate diagrams have been reported for other solutions of water-soluble polymers. Some of these polymers are similar to the type mentioned by the author. Generally, the shear stress-shear rate is a non-linear function for these solutions. Data for plotting apparent viscosity vs shear rate can be obtained from this function. Apparent viscosity is defined as the ratio of shear stress to shear rate at a given shear rate. When plotted, the apparent viscosity decreases with increasing shear rate. This behavior is typical of a pseudoplastic fluid. For some water-soluble polymer solutions, the apparent viscosity decreases more than 50 times while the shear rate increases 1,000 times. Thus, viscosity of a pseudoplastic fluid only has meaning at a specified shear rate. Results of Fig. 1 could be explained in these terms. Viscosities measured in the Ostwald viscometer represent values at a given shear rate. Some average shear rate is affecting the polymer solutions while flowing through the core. This average value fixes the apparent viscosity as long as the flow rate remains constant. Viscosities measured by the two methods will be equal if shear rates are the same. The results indicate that shear rate in the core is lower (higher apparent viscosity) than in the viscometer. In the paper by Johnson, Bossler and Naumann, the relative permeability is independent of viscosity ratio. Thus, the relative permeability with respect to water flow at residual oil should be independent of the flowing phase viscosity. Polymer solutions will appear as Newtonian fluids The discussion emphasizes the nature of the "resistance factor effect" as discussed in the paper. Repeated anomalies arising in hundreds of experiments led us to the conclusion that non-Newtonian flow is not the only factor. Several of the key anomalies are as follows: 1. Measured viscosities over a range of shear rates from <1 sec-&apos; to 1,000 sec-&apos; do not account for but a minor fraction of the R observed in cores when compared in similar shear-rate ranges. 2. The slope of R vs flow rates in cores is always different from that expected from viscometer shear-rate measurements as shown in Fig. 2. in a core, the level of viscosity being fixed at a given flow rate. With these conditions, the definition of resistance factor R by Eq. 2 is simplified to Since , is constant with rate, R becomes a measure of the apparent viscosity in a core at a given flow rate. Variation in flow rate could easily account for the changes of R shown in Fig. 5. Also, this points to the fallacy of assuming R to be a unique parameter. The constant resistance factors at different flooding velocities appear to be in disagreement with the above discussion. The author furnishes Fig. 2 to support his arguments. As shown, the resistance factors remained substantially constant in the two cores over a considerable range of flooding velocities. However, in the 73-md core, the factor increases at lower rates. This behavior agrees with known characteristics of some pseudoplastic material. These materials act both as Newtonian and as non-Newtonian fluids in different regions of shear rate. Some exhibit first Newtonian, then non-Newtonian, finally, Newtonian character. Others are first non-Newtonian and then Newtonian. This latter type would explain the results with the 73-md core. The Fann-instrument results are not significant since shear rates in the core may be much different than with the viscometer. The higher resistance factor at high rates in the 150-md core is more difficult to explain. The greater resistance at increased flow rates could be attributed to what might be termed temporary bridging. As envisioned, changes in polymer configuration occur at the higher energy associated with the increased flow rate. These changes could cause less effective passage of polymer through the core. Correspondingly, increases in pressure drop will occur. These will be interpreted as higher resistance factors. 3. Most polymer solutions are non-Newtonian and many are more shear-rate sensitive than the polymers in question, yet only a very few polymers demonstrate useful R values. Gogarty&apos;s assumption that viscosities in cores and vis-cometers will be the same if measured at the same shear rate is only valid if non-Newtonian rheology is the only parameter. The experimental evidence does not validate this assumption. The anomalies observed in the equilibrium displacement experiment shown in Fig. 5 are not explained on the basis of varying flow rates since the rates were held constant. M

Jan 1, 1965