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John Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—After looking over the authors' shoulders for several years and after many discussions on the interesting diagrams of the types shown, it is a pleasure to see a formal paper published on this subject. There can be no doubt of the practical usefulness of the concepts shown. Inclusion formation in steel is such a highly complex matter that any system for understanding the subject is bound to be welcomed by those who must work with steels and who see in their day-to-day experience the good and evil effects of inclusions. A feature of the work with which the discusser has been concerned, and which he would now like to attempt to explain, is the relation between the schematic diagrams which the authors use and the phase diagrams for related systems. Obviously, the authors' diagrams are in no sense complete phase diagrams. However, there is a relation between this type of diagram and the true phase diagram, and the understand- ing of this relation ought to help in understanding the general picture which the authors are presenting. Consider the authors' Fig. 4, which shows the liqui-dus relations in the Fe-Mn-S-0 system. To show the complete relations between temperature and composition in these four ternary systems would require four triangular prisms, the vertical axes of which would represent temperature. The four triangles of Fig. 4 represent basal projections of certain lines from the four prismatic phase diagrams. Readers of the paper are all more or less acquainted with this type of projection and its usefulness and limitations are generally understood. In order to concentrate on the interesting parts and to minimize the less interesting features, the composition scale may be shifted to de-emphasize regions containing gaseous sulphur and oxygen. Such a diagram is shown in Fig. 16, which is a distorted version of the authors' Fig. 4. Here the oxide of iron is wiistite, denoted by W, and it is to be noted that between W and MnO lies the entire MnO-FeO "binary" system. Similarly, between MnS and FeS lies another binary whose

Jan 1, 1956

By Robert Abbott

THE influence of various elements in retarding or accelerating the absorption of carbon during the process of carburization is fairly well known. In general those elements which forth carbides accelerate the absorption, while those which do not retard it. It has sometimes been wrongly stated that those elements which raise the temperature of the critical range increase the absorption, while those which lower this temperature decrease it. Silicon is a notable exception to this rule, for its influence is to raise the critical range but to lower the absorption of carbon. Some elements which do not form carbides have no apparent influence upon the absorption rate. Carbon itself retards the absorption rate. With a view to obtaining more exact data upon the subject the following experiments were undertaken : 208 steels of different chemical composition were selected to represent most of the types of modern constructional steels. Specimens 3 in. in diameter and in. in length were weighed to milligrams. They were then packed in the special carburizing box shown in Fig. 1, and kept in .the furnace for 10 hours at a temperature of 900° C. A duplicate experiment was conducted at 1,000° C. At equal' intervals of time the box was rotated in the furnace so that. two complete revolutions were made in the 10 hours. This precaution was taken to neutralize as much as possible any effect of unequal heating. At the end of the 10 hours the box was allowed to cool in the furnace with the doors open. The specimens were then weighed again and the increased weight (carbon) determined. In. the following table are given the analyses of the various steels, together with the. increased weight of .carbon expressed in milligrams.

Jan 10, 1913

By Robert R. Abbott

The influence of various elements in retarding or accelerating the absorption of carbon during the process of carburization is fairly well known. In general those elements which form carbides accelerate the absorption, while those which do not retard it. It has sometimes been wrongly stated that those elements which raise the temperature of the critical range increase the absorption, while those which lower this temperature decrease it. Silicon is a notable exception to this rule, for its influence is to raise the critical range but to lower the absorption of carbon. Some elements which do not form carbides have no apparent influence upon the absorption rate. Carbon itself retards the absorption rate. With a view to obtaining more exact data upon the subject the following experiments were undertaken: 208 steels of different chemical composition were selected to represent most of the types of modern constructional steels. Specimens 2 in. in diameter and 9 in. in length were weighed to milligrams. They were then packed in the special carburizing box shown in Fig. 1, and kept in the furnace for 10 hours at a temperature of 900' C. A duplicate experiment was conducted at 1,000° C. At equal intervals of time the box was rotated in the furnace so that two complete revolutions were made in the 10 hours. This precaution was taken to neutralize as much as possible any effect of unequal heating. At the end of the 10 hours the box was allowed to cool in the furnace with the doors open. The specimens were then weighed again and the increased weight (carbon) determined. In the following table are given the analyses of the various steels, together with the increased weight of carbon expressed in milligrams.

Jan 1, 1914

By Edward Martinez

Although the copper segregation process has been known as a method for treating oxide copper ores since the 1920's, the reactions involved in this process are still a matter of conjecture. However, the evidence turned up in a recent series of experiments at Asarco's Central Research Laboratories strongly indicates that some of the proposed reactions may not be occurring. Experimental work on oxide copper ores from the Sagasca mines in Chile led to the discovery of the copper segregation process in 1923. It was found that the reduction of the copper with coal at about 700°C occurred on the surface of the coal instead of remaining disseminated in the ore. The unusual behavior of the copper, which caused it to migrate from the ore particles to the coal, was traced to the presence of a small quantity of sodium chloride occurring in the ore. Further experiments with oxide copper ores proved that the presence of a halide, either occurring naturally or admixed with the ore, caused the copper to migrate from the ore particles and to segregate in the charge.

Jan 8, 1966

By T. Egleston

The importance of making analyses of gases in furnaces which are used for metallurgical purposes is every day growing more and more evident. It is the only method of understanding the reactions that take place in the furnace, and of economically conducting the operations both with regard to the fuel used and the reactions which take place on the bodies to be subjected to the influence of the heat and gases. As a knowledge of the composition of gases is becoming every day more necessary to the proper conduct of furnace operations, it seems desirable that furnace managers should generally know that the analysis of gas for commercial purposes is neither difficult, tedious, or expensive, and that it does not necessarily imply the use of corrections requiring difficult instrumental observations and long and tedious mathematical calculations. Any method, therefore, which will tend to render these analyses simple will also tend to having them made and repeated as frequently as the analyses of the ores and other materials charged in the furnace. They should be made even more frequently, as their composition is affected by any change in the condition of the furnace, and a knowledge of their composition will give a ready clue to the unseen and otherwise not easily detected changes which are taking place. The only practicable method of making industrial analyses of gas is that of measuring volumes in graduated tubes. The methods by

By T. PH. D. Egleston

THE importance of making analyses of gases in furnaces which are used for metallurgical purposes is every day growing more and more evident. It is the only method of understanding the reactions that take place in the furnace, and of economically conducting the operations both with regard to the fuel used and the reactions which take place on the bodies to be subjected to the influence of the heat and gases. As a knowledge of the composition of gases is becoming every day more necessary to the proper conduct of furnace operations, it seems desirable that furnace managers should generally know that the analysis of gas for commercial purposes is neither difficult, tedious, or expensive, and that it does not necessarily imply the use of corrections requiring difficult instrumental observations and long and tedious mathematical calculations. Any method, therefore, which will tend to render these analyses simple will also tend to having them made and repeated as frequently as the analyses of the ores and other materials charged in the furnace. They should be made even more frequently, as their composition is affected by any change in the condition of the furnace, and a knowledge of their composition will give a ready clue to the unseen and otherwise not easily detected changes which are taking place. The only practicable method of making industrial analyses of gas is that of measuring volumes in graduated tubes. The methods by

Jan 1, 1877

By E. H. Roberts, L. G. Swenson, F. C. Nix, R. A. Morgen

The binary system lead-antimony has been the subject of comprehensive investigations in these laboratories by Dean1 and his associates. The effect of a third constituent on this system, particularly on the lead-rich alloys in which dispersion hardening was found, has a commercial value as well as an academic interest. This paper covers the effect of the addition of copper, bismuth and tin, all of which are likely to be found in commercial lead-antimony alloys, and is divided into three parts, as follows: I. The System Lead-A~ili~r~ony-Copper II. The System Lead-Antimony-Bismuth III. The Lead Corner of the System Lead-Antimony-Ti11 These three systerrls are of three different types, and hence may be considered as covering three general kinds of additions. Bismuth forms no compounds with either lead or antimony and forms solid solutions with both. Copper forms several compounds with antimony as well as solid solutions but with lead it forms a two liquid layer system and no appreciable solid solution. Tin is soluble in both lead and antimony in the solid state and also forms a compound with antimony. The effect of small amounts of bismuth on the lead-antimony alloys is small, having no appreciable effect on the solubility of antimony. The temperature of the solidus floor is lowered appreciably by the presence of bismuth, cutting down the range of heat treatment. Copper, on the other hand, due to compound formation, increases the apparent solubility of antimony. The excess antimony is tied up with the copper finally and so is not available for dispersion hardening. The net result of addition of small amounts of copper is to shift the dispersion hardening peak of the

By E. W. Hart, W. R. Hibbard

The room temperature flow characteristics of a series of Cu-Cr alloys are found to be related to the amount and characteristics of the chromium-rich precipitate. The results are consistent with the theory of Fisher, Hart, and Pry, which considers the trapping to dislocation loops around precipitate particles. THE use of dispersed phases for hardening metals, particularly high temperature alloys, has been practiced for several years. Current theories describing the effects of dispersions on the basis of dislocation theory have been proposed by Mott and Nabarro.l-4 rowan," and Fisher, Hart, and Pry.8 These theories recently have been discussed by Hart,' who pointed out that the experimental data available for comparison with theoretical calculations for overaged alloys are confined to studies by Gensamer, Pearsall, Pellini, and Low,8 Shaw, Sher-by, Starr, and Dorn,9 and some hitherto unpublished data on Cu-Cr alloys which will be described herein. Certain difficulties were associated with the interpretation of the first two studies. Gensamer, Pearsall, Pellini, and Low were concerned principally with interparticle spacing and did not document particle sizes. Shaw, Sherby, Starr, and Dorn included all the data in their report which was necessary for the theoretical evaluation, but their study is subject to some question1" due to difference in prior history of various specimens and due to systematic differences in particle characteristics" which appeared to be associated with differences in the magnification of their microscopic examination. The current study was undertaken to obtain critical data in a manner which avoids some of these limitations. Specimens of eight Cu-Cr alloys remaining from a previous investigation'' were available in the form of 100 mil sheet of the compositions shown in Table I. At 200 mil this material had been previously an- nealed ½ hr at 1000°C, water quenched, and cold rolled 50 pct. Samples were further cold rolled to a thickness of 20 mil for a total reduction of 90 pct. Sheet tensile specimens of standard geometry with a gage length 2½ in. long and 0.20 in. wide were machined from this sheet. These specimens were then annealed in a dried N2-H2 atmosphere for the times and temperatures indicated in Table I. This anneal served two purposes: 1—to obtain a fairly uniform and nearly constant grain size of 0.015 to 0.022 mm average diameter, and 2—to precipitate a fairly uniform, nearly spherical over-aged dispersion of essentially pure chromium. A typical microstructure illustrating the grain size and the uniformity of the dispersion is shown in Fig. 1. A typical dispersion illustrating the range of sizes and shapes of the particles is shown in Fig. 2. The tensile specimens were tested in the Instron equipment described in ref. 11 at room temperature at a strain rate of 0.04 in. per in. per min. Three tests were run on each alloy with sufficient repro-ducibility that a single true stress-true plastic strain curve could be drawn through the three sets of data for each alloy. Typical curves are shown in Fig. 3.

Jan 1, 1956

By Frank S. McKenna, Myron A. Pugacz, Clarence E. Jackson

THE notched-bar impact test has proved worth while in certain applications as a test for control of the quality or the heat- . treatment of steel. In view of the serious thought that even so simple a test as the tensile test, has evoked during the past years, it is not surprising that the notched- bar impact test should have inspired much experimental work. The correlation of the great number of data has not been successful, although steady progress has been made toward a better understanding of this test. Progress has been made, especially, in the isolation of the effects of the many variables that control the results. The stress system imposed on a specimen with a notch is so complicated and un- predictable that no simple evaluation of the test has been possible. Because of this uncertainty, many engineers hesitate to use the notched-bar impact test, and this attitude may well continue until a better understanding of the effects of the variables in the test are available. Without doubt, any additional data that may be presented should be accompanied by as complete a description of the details of test as possible, so that it may be added to the general fund of information that is to serve as the basis for the theory of the notched-bar impact test. The many factors that may control the test results have been pointed out repeatedly. The importance of the effect of the type and dimensions of the specimen has been recognized. Most of the work reported by American investigators has been limited to small- size (Charpy) specimens tested as a simple beam; two types of notches (Fig. I) have been commonly used. Considerable data have also been presented by many investigators using a small specimen tested as a cantilever beam; this commonly being called the Izod test. Here, however, a shear component of stress makes the stress system even mare complex than that present in the simple beam type of test, hence a critical analysis is difficult. Much work has also been reported by investigators using the tension type of specimen. A second variable that must be con- trolled is the testing temperature. An indication that the tests were performed at room temperature is not sufficient, since in many steels a variation of a few degrees in the actual testing temperature may be sufficient to give an entirely different range of results. Other factors. such as the com- position and condition of the material being tested and the speed of test, should also be considered. Many investigators have contributed data and theoretical discussions on the problems encountered in notched-bar test-

Jan 1, 1944

By Henry J. Welge

Laboortory apparatus has been devised which permits study of the displacement of oil from cores by water and by gas. The cores used contained interstitial brine as well as oil. Experiments were run to determine the comparative effect of varying the properties of the fluids used. No great effect was noted on the maximum displacement achieved. This observation made it unnecessary in initial work to use fluids in their exact reservoir conditions. Consequently, the displacements were run at near-atmospheric pressure in Pyrex glass equipment, using stripped crude oils. Introduction and Theory The chief object of this work has been to determine the efficiency of gas and water as primary agents for displacing oil from reservoir rock under laboratory conditions in which capillary phenomena were predominant. To this end the maximum displacement of oil from cores has been ascertained. This maximum displacement may not be equal to the maximum displacement from a reservoir; but it will be a close approxirnation to it sometimes, and other times the laboratory information will be useful in reservoir engineering predictions. It is] believed that the laboratory experimental maximum represents the upper limit for the reservoir recovery. The experiments were carried out by obtaining cores of interest from the reservoir, and filling the pores with interstitial brine and oil with the restored state tech- nique.1 Then the oil was displaced from the core as described later, either by brine from below, or by gas from above. The former type of displacement suggests analogy to production by water drive, but not to water flooding, for reasons discussed below. The latter type of displacement is believed to simulate production by gas cap displacement. The displacements were performed by what may be termed the capillary-pressure method. The cores are placed in capillary contact with an oil-wetted membrane which has very small pores (about I micron in diameter). Pores of this size will transmit oil but Prevent the Passage of gas or water, unless the Pressures used are higher than the capillary Pressures employed in this work. Accordingly, use of the membrane makes it possible to apply a capillary pressure differential between the displacing phase and the oil in the core. AS in the displacement of brine toward that condition of oil and water distribution existing originally in the reservoir,' it may not always be desirable to reduce the oil saturation in this experiment to an absolute minimum. With reservoirs having small productive closure, it is preferable to evaluate and use a displacing pressure no higher than the capillary pressure, Ap, which will ultimately become available for displacement in the reservoir. This pressure may be calculated from a knowledge of the density of the oil-in-place, do, the density of the displacing phase, dl, and Ah, the vertical distance between the section of the

Jan 1, 1949

By R. P. Heuer

In recent years an increasing amount of research work has been done on refractory materials for use in copper-smelting furnaces. A few of the larger refractories manufacturers have erected special research laboratories which are fully equipped to study the refractory problems of the smelter. A typical laboratory of this type was described in the January, 1929, issue of Mining and Metallurgy, in an article entitled "Methods of Research Newly Applied to Refractories," by W. F. Boericke. This particular laboratory is equipped for the manufacture of full-size refractory brick. It aims to study on a fairly large scale the behavior of various refractory raw materials and the effect of improved methods of manufacture. The refractories manufacturer has at his disposal the naturally occurring refractory oxides in various degrees of purity, mixed or combined with other oxides. In order to supply the copper smelter with a refractory brick that will permit the most economical operation of the smelting furnaces, it is necessary to have the optimum combination of a number of both physical and chemical properties in the brick. Unfortunately, nature has not provided any raw materials in which the perfect combination of these properties exists. It is, therefore, a problem for man's ingenuity to seek out the most desirable raw materials and develop methods of manufacture that give, in the resultant product, the necessary combination of properties in as full a measure as is possible. In the laboratory it is possible to carry out fairly broad experiments with this objective. It is first necessary to obtain and process the raw materials, then to manufacture them into brick and finally, to test these bricks under conditions designed to interpret or simulate in the laboratory the actual conditions in the smelting furnace. It is necessary for the research engineers to determine certain fundamental properties in the brick which may be subjected to laboratory measurements and to interpret these measurements in terms of brick performance in smelting-plant practice. Such procedure is not what might be called an exact, scientific one but it has been found that great progress can be made when these principles are applied. For example, the resistance of refractory brick to spalling and thermal change can be related to the thermal expansion of the refractory, its thermal conductivity and heat capacity and its

Jan 1, 1934

By S. Saito, P. A. Beck

The crystal structure of MoNi3 was determined by means of X-ray diffraction. This structure is isotype with that of ovgered TiCu3. The lattice parameters are: a. = 5.064A, bo = 4.224A, co = 4.448A, and zf 0.157. If the orthorhombic distortion (slight relative to the corresponding orthohexagonal unit cell) is disregarded, the structure may be described in terms of a close-packed ordered atomic layer, stacked in the sequence: abab. The structztres of ordered TiCu3 and TiAl3 are homotectic. The three types of ordered hexagonal phases, iso-structural with TiNi3, MgCd3, and VCo3, are known to occur in AB3 alloys of transition elements of the first, second, ad third long periods. It was noted1 that phases with the TiNi3 structure occur selectively in alloys of Ti-group elements with Ni-group elements. In AB3 alloys of Ti-group and V-group elements with Co-group elements the AuCu3-type structure predominates.' The vCO3 structure, which was determined very recently,' has hexagonal symmetry, but the actual atomic arrangement here, too, is rather closely related to the ordered cubic structure of AuCu3-type. However, an ordered hexagonal close-packed structure of the MgCd3-type occurs in MOCO33 and WCO3.4 Consequently, the question arises as to whether or not the crystal structure of MoNi3 is also of the MgCd3-type. Grube and winkler5 found that MoNi3 has a hexagonal close-packed structure with a = 2.54A and c/a = 1.65. They pointed out that some additional weak diffraction lines could be observed in the powder pattern, which may have been due to an ordered atomic arrangement in this phase. However, no detailed information was obtained by them and the structure was apparently not further investigated by others. The present work was, therefore, undertaken in an attempt to determine in detail the structure of MoNi3, and to investigate the possibility of ordering. EXPERIMENTAL METHODS Alloys used in the present work were arc-melted in a water-cooled copper crucible under helium atmosphere. Electrolytic nickel and molybdenum, both 99.9 pct pure, were used. Chemical analyses were not made, but the melting loss was not higher than 2 pct for any alloy. Ingots were first homogenized at 1200°C for 48hr, quenched, heavily cold worked, and then annealed at 820" or 860°C for 1 week, followed by quenching in cold water. Powder specimens for X-ray work were prepared by crushing the heat-treated solid specimens. In order to remove strains, the powders were reannealed in evacuated scaled fused silica capsules for 6 hr at the same temperature at which the corresponding solid specimens were annealed. X-ray photographs were taken with an asymmetric focussing camera, using unfiltered CrK or CuK radiation. EXPERIMENTAL RESULTS The X-ray diffraction patterns of alloys containing 20.8, 25, and 26.4 at. pct Mo, homogenized at 1200°C, showed the face-centered-cubic structure of the Ni-base a-solid solution. It was revealed, however, by micrographic examination that the 26.4 at. pct Mo alloy contained in addition very small amounts of a second phase, in accordance with the phase diagram.6 On the other hand, the 20.8 at. pct Mo alloy after annealing at 820°C gave the X-ray diffraction pattern of the ordered face-centered-tetragonal MONi4.7 In this pattern several additional weak diffraction lines were also observed, corresponding to the strongest diffraction lines of MoNi3. The alloys containing 25 and 26.4 at. pct Mo after annealing at 820" or 860°C gave X-ray diffraction patterns, as shown in Tables I and 11, corresponding to MoNi3. Each one of the reflections which could be tentatively indexed on the hexagonal close-packed cell of Grube and Winkler,5 with the exception of the basal plane reflections, was split into a doublet, as seen in Table I. Since microscopically the alloy consisted of a single phase, it seemed probable that the lattice of MoNi3 is actually slightly deformed, as compared with the tentative hexagonal unit cell. In addition to these diffraction lines, several weak lines were also present, as shown in Table 11, which could not be indexed at all on the hexagonal close-packed cell considered. Satisfactory indexing of all diffraction lines observed was found to be possible by using an orthorhombic unit cell with ao = 5.064A, ft = 4.224A, and c = 4.448A. These values, whose accuracy is estimated to approximately ± 0.008A, correspond to 95.14A3 for the volume of the unit cell, and to an X-ray density of 9.50 g per cm3. If no attention were paid to the weak reflections listed in Table II, a reduced -unit cell of half the volume (a = 2.532A, b = 4.448A, and c = 4.224A), closely related to the orthohexagonal cell, might be used. The dimensions of the orthohexagonal cell of the same volume as the reduced cell are: a = 2.562A, b = 4.437 A, and c = 4.183A. It may be seen that in the reduced cell the a axis is slightly shorter, while the b and c axes are slightly longer than those corresponding to the orthohexagonal cell of the same volume. This slight orthorhombic distortion is re-

Jan 1, 1960

By Coopers &. Lybrand

INTRODUCTION From a tax viewpoint, United States mining companies are at a substantial disadvantage in the international mining area compared with companies in other major capital-exporting countries, according to a 1975 study by Coopers & Lybrand for the American Mining Congress. The study compared the relative tax position of a United States investor with investors from Belgium, Canada, France, Germany, Japan, the Netherlands, Switzerland, and the United Kingdom. The comparison was based on average rates of return realizable by investor companies on four mine-model investments in twelve capital-importing countries. The countries in which these investments were assumed to be made are varied in their tax systems so that a wide range of possibilities was included in the analyses. Each mine model was standard so that the rates of return for each investment by each investor were affected solely by the respective tax systems of the capital-exporting and capital-importing countries. UNITED STATES POSITION The study found that the United States competitive position, in terms of the average rate of return on an overall basis, ranked next to last among the nine capital-exporting countries in the study. Further, the United States overall rate of return is more than 20% below that of the country (Japan) with the highest overall rate of return. On an average return-on-equity basis, the United States' position among the nine investor countries, for each of the mine investments studied, was: copper, eighth; iron ore, sixth; nickel, fifth; manganese, a tie for last place. Figure 1 shows the overall results realized by each capital-exporting country on the basis of average return on equity. [ ] The frequency with which a given capital-exporting country attains the highest or next highest rate of return in a capital-importing country provides further insight and another basis for comparing the tax laws of the capital-exporting countries. Of the situations compared in the study, the United States never attained the highest rate of return, and reached the second and third highest rate of return in only two instances. The tables showing the frequencies of rankings are given in Table 1 for each of the four mine models. In summary, the United States mining company does not have a competitive advantage under the tax rules when competing for mineral concessions in other countries. The United States company, in fact, appears to be at a clear disadvantage. The study also considered the effect of the following recent tax proposals on United States investors in international mining ventures:

Jan 1, 1985

By J. E. Strassner

Oilfield emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases. Adding inorganic acids and bases radically changes the physical properties of these films and their emulsion-stabilizing properties. Interfacial films show one of three different physical characteristics when retracted in pendent drop tests. These compressed films have rigid, soap-type or minimum film properties depending on the quantity of asphaltenes and resins in the crude oil and on the pH and composition of the brine. There exists for each crude oil-brine system an optimum pH range over which the adsorbed film exhibits minimum contracted filtn properties. In this range, intmfacial tension is high — frequently near its maximum value — indicating the absence of highly surface-active specier; crude oil-brine emulsions generally show minimum stability; and surfactant requirements for breaking these emulsions are significantly reduced — sometimes no surfactant is needed. About two-thirds of the world's crude oil is produced as emulsions that must be treated (demulsified) to be marketed.' Approximately three-fourths of all domestic crude oil produced must be treated. The percentage of crude requiring treatment increases as fields become older and more water is produced. Demulsification most frequently is attained through use of surfactants, heat and electric treaters. It is estimated that over 75 percent of all oilfield emulsions are broken by chemicals generally containing alkylene oxide condensates. Although acids and bases are known to affect emulsion stability:-' they rarely are used in the oil field except in batch treatment of the most severe emulsions. Nevertheless, pH adjustment by using acids or bases in demulsification has some advantages over other methods. Mainly, it is cheaper. Acids and bases frequently are cheaper to use than surfactants, or can appreciably reduce the amount of surfactant required for demulsification. Secondary advantages are that less oil is lost by emulsi-fication into the aqueous phase, and that less corrosion is encountered when the optimum pH is basic. Limitations to the use of pH include (1) use in brines containing high concentrations of reactive ions, (2) closer supervision for pH control than is required for surfactants and (3) need for corrosion protection when the optimum pH is sufficiently acidic. These factors indicate that the economics of pH con trol in demulsification will be maximized when relatively large treating facilities are needed, when relatively large surfactant concentrations are required to break an emulsion, when a relatively low concentration of the aqueous phase is emulsified in the oil and when the emulsified aqueous phase contains relatively low concentrations of reactive ions. Because there are no broad guide lines for using pH control in breaking oillield emulsions (and because the limited guides available are highly specific and frequently contradictory), this paper will attempt to clarify the principles involved in using acids and bases to break emulsions. These principles also should be useful in refinery separations and in other oilfield applications where stable or unstable petroleum emulsions are involved. Principles of Emulsion Stability Oilfield emulsions generally occur as water droplets dispersed in oil (w/o) and occasionally as oil droplets in water (o/w). These emulsion droplets are usually in the 0.1- to 10-micron range. However, more coarsely dispersed water droplets frequently are present in the emulsion. Pure hydrocarbons and water will not form stable emulsii except in extreme dilutions where the large distance brtween droplets inhibits coalescence. An emulsion breaks because interfacial tension acts to minimize the surface area of the dispersed drops by coalescence. However, emulsions can be stablized for long periods of time by the presence of a third phase that adsorbs at the oil-water interface and inhibits coalescence of the dispersed phase."' Emulsions generally are stabilized by (1) repulsive charges on the surfaces of the dispersed phase and (2) adsorbed films that, being preferentially wetted by the continuous phase, act as a physical barrier to inhibit contact between the dispersed droplets. Both these factors generally are important in stabilizing and in breaking o/w emulsions. However, repulsive charges are less effective in stabilizing w/o emulsions which generally are stabilized by adsorbed films.V or this reason the nature and importance of these films at oil-water interfaces were examined closely; as will be shown, pH changes were found to affect the films significantly, and this work led to laboratory tests of pH- adjustment in emulsion breaking. This paper will present evidence to show that emulsions are stabilized primarily by films that form around droplets

Jan 1, 1969

By Frederick Laist

While remodeling No. 1 section of the concentrator at the Washoe Reduction Works of the Anaconda Copper Mining Co. during the summer of 1912, for the purpose of ascertaining what additional metal recoveries could be made by improvements in concentration practice which had been developed by the staff of the Boston & Montana Reduction Department, at Great Falls, it was deemed advisable to carry on some experiments on the treatment of the regular mill tailings by roasting and leaching, to see whether the losses of metal values might not be still further decreased. In the course of these experiments about 5,000 tons of tailings were roasted, and of the resulting calcine about 200 tons were leached. The results were so satisfactory that it was decided to continue the work on a larger scale, particularly as regards the leaching end of the process, and construction work on an 80-ton roasting and leaching plant was accordingly commenced during the latter part of February, 1913, and is being pushed as rapidly as possible. 80-Ton Leaching Plant. This plant will consist of one 20-ft. roasting furnace of the Mac-Dougall type, specially adapted to the work of roasting for leaching; two leaching tanks, 32 ft. in diameter by 12 ft. deep, together with the necessary solution tanks, air lifts, precipitating launders, etc. It has been decided to precipitate the copper from solution on scrap iron, so as not to hamper the roasting and leaching departments by any weakness that might develop in the precipitating department. It is, however, the intention to experiment with a number of different methods of precipitation; for example, by electrolysis and by hydrogen sulphide. The acid required for the operation of this plant will be purchased, ad the quantity required is not sufficient to justify the installation of an acid plant. An acid plant will, however, be established in con-

Jan 1, 1914

By R. T. Keyes, R. B. Clay, L. L. Udy, V. O. Cook, M. A. Cook

Based on compressibility and stress wave velocity in rock, initial explosive loading conditions, the thermochemistry of the explosive and reasonable description of the pressure-distance relations behind the shock front, the distribution of energy between the products of detonation and the burden are estimated as a function of time for various loading conditions. These include 'powder factor', loading density A (fraction of borehole occupied by explosive), and the explosive itself. Factors responsible for rock fragmentation are discussed in terms of: 1) 'release wave fracturing', 2) 'shear wave fracturing', and 3) 'release of loading fracturing' or 'rock bursting'. Release wave fracturing appears to occur only in the immediate vicinity of free faces, and shear wave fracturing only adjacent to the borehole under normal blasting conditions. Rock bursting is thus considered to be the most important means of rock fracturing in blasting. Means for maximizing it are considered. The most important factors to consider include maximum available energy A, explosive density p1, loading density A and 'powder factor'. Maximum efficiency is attained in general by maximizing the A . p1 product. This is achieved by using high density explosives at a loading density of unity (A = 1.0). Ways for achieving this condition are discussed. The bulk-handled aluminized slurry blasting agents have the desired properties for achieving optimum conditions for high blasting efficiency based on the theory outlined herein. Factors considered most important in the blasting of rock are: 1) The maximum available energy A, determined by the heat of explosion Q and the mechanical efficiency ?, a factor intimately associated with the mode of application (A = Q at highest gas concentrations). 2) The 'borehole pressure', pb, or the maximum pressure developed in the borehole after passage of the detonation wave and before the burden has had time to move or become compressed appreciably. (Owing to the short duration of the detonation wave at any particular point in the borehole, the fact that the explosive may not always fill the borehole completely and the further fact that the burden may not actually see the detonation pressure, the borehole pressure is considered more significant than the detonation pressure p2 as a performance factor in borehole blasting.) The borehole pressure is determined by the explosion or adiabatic pressure, p3 , and the loading density, A, or the fraction of the borehole filled by explosive. 3) The physical conditions important in the application of the explosive are: a) The 'powder factor,' (We/Wr), or the ratio of the wt of the explosive to that of the rock being blasted expressed as lb per ton or more generally in lb/cu yd. b) The bulk density, p1 ?. c) The 'burden' or 'line of least resistance,' the spacing between boreholes, the geometry of the borehole pattern and sequence of firing. d) The physical and chemical properties of the rock, most significant of which are possible heterogeneties, such as faulting, prefracture, and greater than micro-scale chemical heterogeneities. (This factor is not considered here but deserves a great deal of careful consideration.) All of these factors need to be carefully considered in the most economical engineering of a blast. Here is considered firstly an outline of the present status of dynamic rock mechanics, particularly as it pertains to blasting. The factors pertaining to the most efficient application of blasting agents are also considered, followed by a discussion of methods of application to achieve optimum explosives performance. ROCK MECHANICS Dynamic rock mechanics is currently a rapidly developing science contributing greatly to a better understanding and consequently the more effective application of explosives in blasting of rock.1-22 Basic to the development of the science of dynamic rock mechanics were the advances of Goransen23 and the Los Alamos and NOL groups24-28 concerning rock and stress wave phenomena and the transmission and reflection characteristics of stress waves at interfaces between different media. Basing considerations on this new knowledge as well as new experimental methods of study (ultra-high speed streak and framing cameras and electronic timers) the theory of fracture and failure of solids under impulsive loading by stress waves developed rapidly.14,16,27-29 Also the

Jan 1, 1967

By Frank Alfred Fahrenwald

A complete list of the elements as given for 1915 includes 18 that melt above 1,700" C. There does not exist one complete thermal equilibrium diagram for any pair of these 18 elements. Several of these elements have been combined, in relatively small proportions, with metals of lower melting point: e.g., tungsten, molybdenum, and vanadium, in steels, or with nickel and cobalt; but of this refractory group, platinum is the only one that has been extensively studied in this connection. When one considers that, with few exceptions, the industries have made use of alloys to the exclusion of pure metals, it is reasonable to expect that alloys of this refractory group will invade fields in which the pure metals have found little application. The past neglect of this class of metals has, no doubt, been partly due to the rarity of some of them, for even though alloys of very valuable properties should be developed, their cost, unless in exceptional applications, would be prohibitive. There is also a well-founded reluctance to undertake research involving very high temperatures which, in the case of most of these elements, must be accompanied by an inert atmosphere as well. This combination of high temperatures*and control of atmosphere within the heating chamber of any furnace of present design is a difficult problem. It is the purpose of this paper to give results,' of an investigation of one binary series of this group, in which methods were employed that avoided the usual difficulties accompanying high-temperature alloy investigation. , Historical.—The alloys of tungsten and molybdenum have received very little consideration during the past. A review of available literature reveals very little regarding this system, and that which has been recorded seems to be at fault. Mennicke2 writes, "Die bekannteste Verbindung

Jan 1, 1917

By Chas. Y. Clayton, Francis B. Foley, W. E. Remmers

DuRing the summer of 1919, the late Dr. Henry M. Howe, then Chairman of the Division of Engineering of the National Research Council, organized a committee to obtain a better insight into the behavior of carbon steels under the influence of various treatments by a proper control of the time and temperature factors. During part of 1919 and 1920, work in connection with this investigation was carried on at Dr. Howe's laboratory at Bedford Hills, N. Y. During 1921 there was an enforced hiatus in the work, occasioned by the illness which resulted in Dr. Howe's death in 1922. At that time one of the present authors compiled the results of the work which had been done and this was published in 1923.' Following the publication of this work, it seemed desirable to carry on in the same manner an investigation of steel of C 0.75 per cent., which steel had not been as fully treated as had the other steels of C 0.34 and 0.52 per cent., used in the published work. Furthermore, certain unusual results have been obtained in the treatment of C 0.52 per cent. steel by quenching and drawing, and repetition of this part of the work seemed advisable. This has been done during the past year at the School of Mines and Metallurgy of the University of Missouri at Rolla, Mo., by a cooperative undertaking of the School and the Bureau of Mines, working in conjunction with the Committee on Heat Treatment of Carbon Steels of the National Research Council. The present paper is a report of the results obtained in this work.

Jan 1, 1926

By L. E. Wilsey, W. G. Bearden

This paper presents results of analysis of the effect of fracturing on initial flow rates and on ultimate recoveries from low capacity oil formations. This analysis shows that even in formations of permeability as low as 0.1 md, large fracture treatments can yield oil recoveries and production rates approaching those of high permeability formations. Field production information is shown which supports the analytical work. INTRODUCTION Often hydrocarbon bearing formations are discovered which, while they are known to contain large quantities of oil, will not produce at commercially attractive rates without special well stimulation. Attempts to solve this problem led to the development of such techniques as underreaming, shooting, acidizing, and recently hydraulic fracturing. These methods of stimulation have been highly successful in many fields. All of these treatments, however, affect only the pay section near the well bore and therefore owe their success to circumventing and overcoming local permeability reduction about the well bore. It has been the belief that in treating wells to stimulate production in which there is no permeability reduction near the well, the maximum possible production rate increase would be of the order of two or fourfold. Hence, it has been concluded that fracture treatment of uniformly low capacity (permeability times thickness) formations could meet with but limited success. It is the purpose of this paper to show that the use of fracture treatments much larger than usually used can yield commercially attractive producing rates and high recoveries even in formations of permeability less than 0.1 of a md. PROCEDURE In order to illustrate the effects of fracturing, an analytical study of some hypothetical systems was made in which one factor at a time was varied to show what is important in recovering oil from fractured wells. It was assumed that a horizontal fracture of relatively high fluid-carrying capacity extended from a well bore. The presence of such a fracture will cause a marked influence on the flow pattern and pressure distribution in the formations, with the net effect being to reduce tremendously the resistance to flow into the well bore. A diagram of the resulting flow pattern and pressure distribution is illustrated in Fig. 1. Immediately after production commences, the principal flow of fluid is vertically from the formation flanking the fracture, into the fracture, and then into the well. After sufficient oil and gas have been produced to lower the pressure in the formation adjacent the fracture, oil and gas will begin to flow in a radial manner into the fracture from the formations beyond the end of the fracture. In calculating the performance under such conditions. the material balance or conservation of matter equation and equations of flow were solved simultaneously by a stepwise method of calculation. Flow rates were found by determining the pressure distribution, as illustrated

Jan 1, 1955

By S. L. Sass

DURING an electron microscope study of the w phase in zirconium-base alloys,1 a stereographic technique was devised which allows the synthesis of high energy electron diffraction patterns from a single crystal containing several variants of a second phase. The technique will be described using as an example the w phase which forms in a bcc matrix. The w phase was suggested by Silcock et al.2 and Bagaryatskii et al.3 to have a hexagonal structure with (0001)111(111)^, [001]B//[110]B* *The subscripts B and 1 are used to refer to the bcc phase and one particular orientation of the w phase, respectively. and with cell parameters aw = v2aB, where a^ is the lattice parameter of the bcc struc-ture. Since there are four <lll>B directions there should be four orientations of the w phase. In approaching this problem the question to be answered is, "What reciprocal lattice vectors from the B phase and the four w variants lie in the particular reciprocal lattice plane of interest?" One may restate the question in the form, "What plane normals from the B phase and the four w variants lie in the particular reciprocal lattice plane of interest?" The question is answered and the desired diffraction patterns are plotted using the following stereographic technique. Knowing the cw/aw ratio (=0.613 for the as-quenched form of the w phase), a stereographic projection of plane normals from one w variant can be constructed relative to a cubic projection using the above orientation relations, with the direction of the projection along the [001]B direction, Fig. 1. Let us now synthesize the diffraction pattern observed by looking along

Jan 1, 1970