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J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp u/RT, where u is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

air-lift and equipped with tapered tubing of proper design, we would have a gas input consumption of about 2500 cu. ft. per bbl., which at 3 to 4c. per 1000 cu. ft. would be 7 1/2 to l0c, per bbl., and there would be very infrequent loss of production due to stoppages. It has been demonstrated that with efficient design of air-gas lift, the production of wells can be increased much beyond that obtained with the former type of air-lift employed; also that small wells can be operated by air-lift with tapered tubing at a cost that places this method in competition with beam pumps in many fields. The next step in conservation that the writer expects to have an opportunity to demonstrate is that of restoring the pressure in a pool and producing by air-gas lift all of the oil possible to lift economically. This combined operation is probably the method toward which we shall eventually be working in recovering the maximum quantity of oil from pools where the oil is recovered through bore holes. General Discussion on the Air-gas Lift H. P. Porter, Tulsa, 0kla.—The papers presented at this meeting contain a great amount of valuable information. Wonderful progress has been shown in the development of air and gas-lifts. There has been nearly everything brought out that touches upon the subject. The real point that is lacking is exact knowledge of the velocity with in the flow column which will produce the best effect—that is the thing we must know more about. Velocity in Gas-lift Flow In other lines of industry the matter of velocity of fluids in pipe lines has been well analyzed and there are known laws by which to calculate velocity of flow; for instance, in irrigation work large pumps are designed with intake pipos to employ an intake velocity of 4 ft. per scc. By reduced cross-sect'ion the velocity is increased rapidly as it enters the pump and the discharge rate is at 12 ft. per src., which in turn is reduced in the discharge column to 4 ft. per sec. Crushed coal, grain and granular material is found to be best conveyed by air when a pneumatic conveyor is employed at 100 ft. per sec. As in the design of a pumping plant or a pneumatic conveyor, the velocity at the lower end of the column in the flowing well must be controlled within certain limits for best results. Mr. Griswold, I believe, stated that they had velocity as low as 15 it. per scc. and from that up to 78 ft. per sec. Mr. Pierce and Mr. Lewis showed an ideal flow column showing how the velocity increased as the fluid was carried up the column, hut did not give any figures as to the velocity. It would be well to take that sort of a diagram to establish an ideal velocity at the lower or intake end, and then calculate the velocity from expansion of the gas as it goes up. It may be that the, ideal intake velocity would vary, depending on the depth of the well, the quantity of liquid to be handled or the pressure which it may be desired to hold. The subject is one that might be worth much research.

Jan 1, 1928

By David H. Browne

The trite maxim that man is a tool-using animal might nowa-days be amended by saying that man is a tool-choosing animal. The chipped flint, at first all-sufficient, gave way to hammered bronze, and that, in turn, to wrought-iron and steel. As our knowledge of metals increases, we learn to specialize; we temper and anneal; we alloy and intermix; and we fashion for ourselves a metal suitable to our necessities. The knowledge of the properties and uses of the various metals and their alloys has become the capital of every constructive engineer, and the currency of every intelligent brass-founder aid blacksmith. Prom year to year, the specifications of the designer become more rigid, and the steel-maker is forced to study more closely the qualities obtainable by changing the treatment, or altering the composition, of his metal. Of making alloys there is no end. We have heard much, during the last decade, of manganese-steel and chrome-steel, of aluminum and tungsten, of titanium- and silicon- and copper-steels, and of every conceivable union into which steel could be coerced or cajoled. Without denying to each of these alloys novel and valuable properties, it. must be admitted that, of all alloys, the one which shows the greatest range of adaptability, and has met the largest measure of popular approval, is nickel-steel. Introduced to public notice by Mr. Riley, in 1889, its field of usefulness has been rapidly enlarged, until, at the present day, the use of nickel-steel is as thoroughly recognized as that of carbon- or manganese-steel. Concerning the properties of nickel-steel numerous articles have appeared in the technical journals. For the man in a hurry, who wishes to look up the properties and limitations of nickel-steel, these articles might almost as well be in the lost

Jan 1, 1900

From the historical account of the coal industry set forth in the preceding pages the reader will have learned that coal is extremely widely spread throughout the United States, and in most places it has been easily found, that it has been remarkably easy to develop, and, where the deposits were available to streams on which it could be transported to markets, it was opened almost as soon as the country was settled. Such were the mines along the James, Susquehanna, Monongahela, Ohio, Kentucky, Cumberland and Big Muddy Rivers. In other localities where such easy means of transport were not convenient, the early production was confined to local use, or to places to which it could be hauled by wagons, but everywhere small mines were established almost as soon as the country was settled, and these increased both in number and size as the available markets grew. These early mines were nearly always opened by local people, and the industry was so far-flung that its growth attracted little or no attention excepting when a labor disturbance or a breakdown in transportation occurred. Had it been concentrated in a few places as most metal industries were, or as the petroleum industry was for many years after it started, it is probable that much better records of its progress would have been kept. When the canal era began, in the eighteen twenties, coal was at first not considered as a valuable source of freight revenue, and much surprise was expressed that the receipts of the Schuylkill Canal were very largely from coal after the first few years, as was the case of the Union Canal though not to such an extent. Even the early railroads to the coal fields did not realize the extent to which the products of mines would figure in their revenues, and it was many years before railroads were built practically solely for prospective coal traffic; indeed this did not happen until some years after the Civil War. Map 12 shows the extent of the canal system in the United States in its relation to the coal fields at the time of its maximum development. It will be seen that only the coal areas in Pennsylvania, Ohio, and to a very small extent in Indiana were able to ship by canal at all, and that only a very small portion of such fields could do so. Looking backward, it is hard to understand the great hopes entertained of canals by their pro-

Jan 1, 1942

By R. K. Dann, L. W. Roberts, R. B. Benson

The mechanical properties of 300-series stainless steels were investigated in both high-pressure hydrogen and helium environments at ambient temperatures. An auslenitic steel which is unstable with respect to formation of strain-induced a (bee) and € (hcp) mar-tensile is embrittled when plastically strained in a hydrogen environment. A stable austenitic steel is not embriltled when tested under the same conditions. The presence of hydrogen causes embrittlement at the mar-lensitic structure and a definite change in the general fracture mode from a ductile to a quasicleavage type. The embrittled martensitic facets are surrounded by a more ductile type fracture which suggests that the presence of hydrogen initiates microcracks at the martensitic structure. If a steel is unstable with respecl to fortnation of strain induced martensile, plastic deformation in a hydrogen environment will produce rapid embrittlement of a notched specimen in comparison to an unnotched one. FERRITIC and martensitic steels can be embrittled by hydrogen that has been introduced into the alloys, either by thermal or cathodic charging prior to testing.1-5 However, conflicting reports exist as to whether austenitic steels that are stable or unstable with respect to formation of strain-induced martensite can be embrittled by hydrogen.8-12 A recent investigation has shown that cathodically-charged thin foils of a stable austenitic steel can be embrittled.13 An earlier investigation of a thermally charged 18-10 stainless steel revealed a significant decrease in the ductility only at the lowest test temperature of -78°C, although strain-induced bee martensite was shown to be present in one specimen tested at ambient temperatures.' When martensitic steels are tested in a hydrogen atmosphere, they are embrittled.'4-'7 It has been observed in this Laboratory that 304L steel, which is unstable with respect to formation of strain induced martensite, forms surface cracks when plastically strained in a high-pressure hydrogen environment. Work in progress elsewhere concurrent with this investigation has also established that 304L is embrittled when tested in a high-pressure hydrogen atmosphere." The objective of this investigation was to study the effect of a high-pressure hydrogen environment on the tensile properties of a stainless steel that contained strain-induced martensite (304L) and one that did not (310). EXPERIMENTAL TECHNIQUES Notched and unnotched cylindrical specimens were machined from 304L* and 310 rods that were heat- treated at 1000°C in argon for 1 hr followed by a water quench. The chemical analyses of these steels are given in Table I. The unnotched specimens had a reduced section diameter of 0.184 & 0.001 in., a gage length of 0.7 in., and were threaded with a 0.5-in.-diam. thread on each end. The notched specimens had a reduced section diameter of 0.260 * 0.001 in. and a 0.75-in. gage length, with a 30 pct 60 deg v-notch at the center. The notch had a maximum root radius of 0.002 in. The tensile bars were fractured in a hydrogen or helium atmosphere of 104 psi at ambient temperatures. The system used for mechanically testing the specimens is to be described in detail elsewhere.19 Several specimens of each type were tested in air using an Instron testing machine. The same yield strength and ultimate tensile strength were obtained in 104 psi helium with the above system as with the conventional testing machine. Magnetic analysis was employed to determine that there was a (bee) martensite in plastically deformed 304L and that it was not present in plastically deformed 310. The magnetic technique depended on allowing the material being studied to serve as the core between a primary and secondary coil. Thus, any change in the amount of magnetic material present between the annealed and plastically deformed steels will be indicated by corresponding changes in the induced voltage in the secondary circuit." The ratio of the output signal of a nonmagnetic stainless steel to a completely magnetic maraging steel was 2000 to I. Several unnotched 304L bars tested in hydrogen were analyzed for hydrogen by vacuum fusion analysis. There was an increase in the hydrogen content to approximately 2 ppm for the specimens tested in hydrogen, as compared to less than 1 ppm for the as-received material. Several thin sections cut from notched areas of 304L specimens tested in hydrogen and containing the fracture surface contained approximately 1.5 ppm H. The accuracy of these determinations was estimated to be ± 50 pct.

Jan 1, 1969

By R. W. Regehr, R. A. Burmeister

Epitaxial growth of GaAs 1-xPx on germanium substrates was achieved using an open tube vapor transport system. The compositional range of 0.3 < x < 0.4 was examined. The best results were obtained with (311) orientation of the germanium substrate. The physical and chemical properties of the resulting layers were investigated using several techniques. Spectrographic analyses of the layers indicate substantial incorporation of germanium into the GaAs t-X Px layer. Evidence is presented which indicates that this incorporation occurs via a vapor phase transport process rather than by solid phase dijfu-sion. Electrical measurements suggest that the germanium thus incorporated behaves predominantly as a deep donor in the compositional range of 0.33 < x * 0.40 and has a deleterious effect upon the luminescent properties of GaAs1-x Px. The increasing technological importance of GaAs1-xPx for use in light-emitting devices has led to an evaluation of several aspects of existing growth processes. The method most commonly used to prepare GaAs1-xPx for electroluminescent device applications is vapor phase epitaxial growth on GaAs substrates.&apos;-4 In a typical electroluminescent diode structure the active region of the diode is entirely within the epitaxial layer and thus the electrical properties of the substrate are relatively unimportant since it is effectively a simple series resistance (assuming hetero-junction effects to be negligible). The use of germanium rather than GaAs as the substrate material is of interest for several reasons. First, GaAs of reasonable structural quality has been epitaxially grown on germanium4-2 and it is reasonable to expect that GaAs1-xPx could subsequently be deposited on the GaAs layer. Second, germanium substrates are readily available with both lower dislocation densities and larger areas than GaAs. Finally, single crystals of germanium are more economical than GaAs single crystals. The principal objective of the present investigation was to test the feasibility of growing GaAs1-xPx epi-taxially on germanium substrates, and to evaluate the properties of such layers with regard to electroluminescent device requirements. The approach used was to a) demonstrate epitaxial growth of GaAs1-xPx on germanium, and b) characterize the relevant structural, electrical, and optical properties of the GaAs1-xPx layers. The possibility of germanium incorporation into the grown layers was of special interest since there was some indication of this in previous studies of GaAs growth on germanium.5&apos;11,12 Although a study of the electrical properties of germanium in GaAs1-xPx was not an intent of this investigation, several features of the electrical properties of the layers grown in the present study which appear to be due to germanium are described. EXPERIMENTAL PROCEDURE The open-tube vapor transport system used for the epitaxial growth of GaAs1-xPx is illustrated in Fig. 1. This system utilizes the GaC1-GaC13 transport reaction and is similar in most respects to the larger system described elsewhere.&apos; The germanium substrates were n-type, with a resistivity of 40 ohm-cm (Eagle-Picher Co.). These were cut to the orientations of {100), {111), and (3111, and were mechanically polished and chemically etched in CP-4 (5 min at 0°C) prior to growth. In some cases, a GaAs substrate was employed in addition to the germanium. The orientation of the latter was {loo}, and they were also mechanically polished and chemically etched prior to growth. The initial composition of the deposited layer was pure GaAs. After approximately 10 microns of GaAs was deposited on the germanium substrate, the phosphorus content of the layer was gradually increased over a distance of approximately 15 microns to the desired concentration and maintained at this value throughout the remainder of the growth. Typical operating parameters used during growth are given in Table I. Selenium was used as a n-type dopant in several runs to facilitate comparison of the electrical properties of the layers grown on germanium with those of layers grown on GaAs substrates, which are usually doped with selenium. The concentration of H2Se in the gas phase was adjusted to a value which would normally yield a carrier density of 1 to 5 x 101 7 at room temperature in layers grown on GaAs substrates. The terminal surfaces of the epitaxial layers were examined by optical microscopy for structural characteristics. Laue back-reflection photographs (Cu radi-ation) were also made on the terminal surface to verify the epitaxial nature of the deposit. After these steps

Jan 1, 1970

By P. Gordon

An isothermal jacket microcalorimeter, supplemented by metallographic, microhardness, and X-ray measurements has been used to study the isothermal annealing of high purity copper after room temperature tensile deformation. The amount of stored energy released during annealing has been measured as a function of deformation in the range 10.8 to 39.5 pct elongation. The data have shown the major heat effect to be associated with recrystallization and have allowed an analysis of the recrystal-lization kinetics and the calculation of activation energies of recrystallization. WHEN a metal is deformed plastically, some of the energy expended is dissipated as heat during the working process, while the remainder is stored within the metal in the form of lattice distortions and imperfections. During subsequent heating of the metal, the distortions and imperfections can be largely annealed out and the associated stored energy released as heat. It is apparent that measurements of the evolution of stored energy during such annealing may produce important information concerning the nature of the annealing mechanisms and the imperfections involved. Some excellent studies of this type have been made in the past, notably those of Taylor and Quinney,&apos; Suzuki,2 Bever and Ticknor,3 Borelius, Berglund, and Sjöberg,4 and Clarebrough et al.5,6 None of this work, however, employed isothermal techniques, with the exception of the Borelius studies&apos; in which only the early annealing stages were investigated. Since isothermal measurements, as compared with heating or cooling curve, have the merits that 1—they reveal the kinetics of a process more clearly, 2—the results obtained are more easily applied to theory, and 3—most fundamental investigations of annealing using techniques other than calorimetry have been carried out isothermally, it was considered important to apply calorimetry to the study of the isothermal annealing of metals. Accordingly, an isothermal jacket calorimeter of the Borelius type,&apos; supplemented by metallographic, hardness, and X-ray measurements, has been used to study the annealing of high purity copper after room temperature tensile deformation. Experimental The microcalorimeter has been described fully elsewhere." Briefly, the specimen to be studied is placed in a constant temperature environment of virtually infinite heat capacity achieved, as shown in the drawing of Fig. 1, by means of a vapor thermostat. A high thermal resistance is provided between the sample and the environment and a sensitive differential thermopile (see Figs. 2 and 3) arranged with half its junctions in contact with, and thus at the constant temperature of, the environment, and the other half in contact with the sample. A reaction in the sample develops a small difference in temperature, AT, across the thermopile, which is followed by a recorder-galvanometer set-up as a function of time, t, and is converted to reaction heat per unit time, P, by the use of the equation AT P=a?T + b AT dt The constants, a and b, in Eq. 1 are determined by a simple calibration, making use of the Peltier heat developed by a small current run through the junction of a thermocouple located in an axial hole in the specimen (Fig. 2). In its present form, the limit of sensitivity of the calorimeter is a heat flow of 0.003 cal per hr. The copper used was the spectroscopically pure metal supplied by the American Smelting and Refining Co. in the form of 3/8 in. diam continuously cast rod, reported to be 99.999+ pct Cu. A small amount of the copper was available at the start of this work and is referred to hereafter as lot A. A second batch, lot B, was obtained later, most of the results described subsequently being for this lot. As will be seen, there is some indication that lot A was somewhat purer than lot B, but it is not known whether this difference was present in the as-received metal or arose during subsequent handling. The two lots of copper were remelted and cast into two 1½ in. diam ingots in vacuo, using high purity graphite crucibles and molds. The ingots were upset several times to break up the large cast grains, and then rolled and swaged to rods 0.391 in. in diameter, using several intermediate anneals with about 40 pct reduction in area between anneals. The penultimate anneal was 2 hr at 350°C. X-ray examination showed no marked general preferred orientation in the resulting rods. The grain structure typical of the two rods is shown in the micrograph of Fig. 4." It was found to be virtually im- possible to get an unambiguous measure of the absolute grain size in the two annealed rods because of the profusion of annealing twins and the lack of regularity of the grain boundaries. However, counts of the number of boundaries intersected per unit length along a random line on a polished section, making a correction for the proportion of boundaries (about half) estimated to be twin boundaries, gave a figure of about 0.015 mm for the average grain diameter. The grain size of the rod from lot A was about 5 pct smaller than that from lot B. The rods were cut into 1 ft long bars and these deformed in tension at room temperature to various total elongations in the range 10.8 to 39.5 pct. A strain rate of 1 pct per min was used. The deformed bars were then stored in a dry ice chest until such time as samples were to be cut from them. Five bars deformed as indicated in Table I were used for the subsequent tests. In all cases, all the calorimeter.

Jan 1, 1956

By F. D. Rosi

The slip and twinning behavior in extended titanium crystals were studied in some detail. The formation and appearance of coarse kink bands are discussed. Their crystallographic geometry was determined by X-ray analysis. A phenomenological interpretation of the complexities in kink band development is also presented. The critical resolved shear stress, coefficient of shear hardening, and plane of fracture were determined for several crystals extended at room temperature. THE slip and twinning elements observed in the room-temperature deformation of titanium were enumerated in a previous paper1 in which considerations were advanced regarding the nature and selection of these elements and their effect on the known mechanical properties of this metal. The present study concerns the crystallographic, microscopic, and mechanical aspects of flow in relation to the slip and twinning elements, and includes a prediction of slip systems, nature of slip and twin markings, inhomogeneities of plastic flow, and stress-strain characteristics. Unless otherwise noted, arc-melted titanium sponge (99.77 pct) was used in these experiments. The method of production of crystals, their dimensions, and the surface preparation for micrographic examination have been reported.&apos; For obtaining stress-strain characteristics, only those crystals which traversed the entire width of the specimen and were at least 8 mm in length were used. Tensile deformation of the crystals was performed with conventional grips for sheet specimens and a constant-stress loading beam, designed after the method of Andrade and Chalmers.&apos; The specimens were loaded by allowing sand to flow from a reservoir into a bucket suspended from the longer end of a balanced 6:1 lever arm at a rate controlled to load the specimen approximately 2 kg per min. Strain measurements were made using the Baldwin SR-4, bonded, resistance-wire strain gage, Type A-8, which permitted a reading accuracy of 2 microinches per inch. The formulas used in the evaluation of shear stress and shear strain, as in deriving the coefficient of shear hardening, are given by Schmid and Boasv n terms of the original orientation and change in length of the crystal. For calculating the critical resolved shear stress, the standard equation was used. The crystallographic nature of the unpredictable slip observed in a number of specimens was determined by the single-surface X-ray method of analysis as described in ref. 1. Experimental Results Prediction of Slip System: It was reported&apos; that room temperature slip in titanium takes place predominantly on {10i0} and in a <1120> direction, giving three potential slip systems. Hence, it should be possible to predict the operative primary system in the manner used by Taylor and Elam&apos; for alu- minum (i.e., the one with the greatest component of shear stress in the direction of slip). The stereo-graphic construction in Fig. 1 shows that this is true. In all cases, slip was found to occur initially on the (0110) plane and, in a number of cases, in the [21f0] direction. (The direction of slip was not determined for all orientations.) It follows that duplex slip can be expected when two slip systems are geometrically equally favorable for slip, as demonstrated in Fig. 2. In both crystals slip took place simultaneously on the (1700) and (olio) prismatic planes, as indicated by Fig. 2a and b. In the case of crystal B the movement of the specimen axis with increasing extension was toward the (10i0) direction, which represents the stable end orientation resulting from alternate slip on the [2ii0] and [1120] directions. This is analogous to the duplex slip process in face-centered cubic metals." Unpredictable Slip: In a number of crystals whose orientations were well within the operation of a single slip system, secondary slip occurred on planes not predicted by the criterion of maximum shear stress. Examples are shown in Fig. 3. In addition to

Jan 1, 1955

By Allan E. Martin, Harold M. Feder, Irving Johnson

The cadmium-uranium system was studied by thermal, metallographic, X-7-ay and sampling techniques; special emphasis was placed on the establishment of the liquidus lines, The single inter metallic phase, identified as the compound UCd11 melts peritectically at 473°C to form a-umnium and melt containing 2.5 wt pct uranium. The cadmium-rich eutectic (0.07 wt pct uranium) freezes at 320.6°C. Solid solubilities in uraizium and cadmium appear to be negligible. Between 473°C and 600°C the liquidus line is retograde. NO publication relating to the cadmium-uranium phase diagram was found in the literature. The establishment of this diagram was of considerable interest to us because of a possible application of the system to the pyrometallurgical reprocessing of nuclear fuels. Analysis of liquid samples, metallographic examination, thermal analysis, and X-ray diffraction analysis were used to establish the phase diagram from about 300° to 670°C. Particular emphasis was placed on the establishment of the liquidus lines. The same system was concurrently studied in this laboratory by the galvanic cell method.&apos; Both studies benefited from a continual interchange of information. MATERIALS AND EXPERIMENTAL PROCEDURES Stick cadmium (99.95 pct Cd, American Smelting and Refining Co.) contained 140 ppm lead as the major impurity. Reactor grade uranium (99.9 pct U, National Lead Co.) was most often used in the form of 20-meshspheres. This form was particularly suitable because it does not oxidize as readily as finer powder. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The liquid sampling technique is described elsewhere2 alumina crucibles (Morganite Triangle RR), tantalum stirring rods, tantalum thermocouple protecthecadmiumtion tubes, Vycor or Pyrex sampling tubes, and grades 60 or 80 porous graphite filters were used. Uranium dissolves in liquid cadmium rather slowly. In order to achieve saturation of the melts it was necessary to modify the procedure of Ref. 2 by the use of more vigorous stirring and longer holding periods (at least 3 hr) at each sampling temperature. The samples were analyzed for uranium by spectro-photometry (dibenzoyl methane method) or by polar- ography. The analyses are estimated to be accurate to 2 pct. Thermal analysis was performed on alloys contained in Morganite alumina crucibles in helium atmospheres. Standard techniques were employed; heating and cooling rates were about 1°C per min. For the determination of the peritectic temperature, Cd-10 pct U charges were first held for at least 50 hr at temperatures in the range 435° to 460°C to form substantial amounts of the intermediate phase. For the determination of the effect of cadmium on the a-p transformation temperature of uranium, charges of Cd-25 pct U (-140+100 mesh uranium spheres) were first held near the transformation temperature, with stirring, to promote solution of cadmium in the solid uranium. The holding times and temperatures for these treatments were 18 hr at 680°C for the cooling run and 28 hr at 630°C for the heating run. Alloy specimens for X-ray diffraction and metallographic examination of the intermediate phase were prepared in sealed, helium-filled Vycor or Pyrex tubes. Ingots from solubility runs and thermal analysis experiments also were examined metallographically. Crystals of the intermediate phase were recovered from certain cadmium-rich alloys by selective dissolution of the matrix in 20 pct ammonium nitrate solution at room temperature. Temperatures were measured with calibrated Pt/Pt-10 pct Rh thermocouples to an estimated accuracy of 0.3°C. However, the depression of the freezing point of cadmium at the eutectic is estimated to be accurate to 0.05°C because a special calibration of the thermocouple was made in place in the equipment with pure cadmium just prior to the measurement. EXPERIMENTAL RESULTS The results of this study were used to construct the cadmium-uranium phase diagram shown in Fig. 1. This diagram is relatively simple; it is characterized by a single intermediate phase, 6 (UCd11), which decomposes peritectically, and which forms a eutectic system with cadmium. The solid solubilities in the terminal phases appear to be negligible. An unusual feature of the diagram is the retrograde slope of the liquidus line above the peritectic temperature. The Liquidus Lines. The liquidus lines above and below the peritectic temperature are based on three separate solubility experiments. The data are shown in Fig. 1 and are given in Table I. It is apparent from the figure that the solubility data obtained by the approach to saturation from higher temperatures fall on substantially the same lines as those obtained

Jan 1, 1962

By W. L. McMorris, A. H. Brisse

IN the last several years the coal industry has intensified its effort to solve the growing problem of cleaning and recovering fine mesh coals. On one hand there has been increasing civic pressure for cleaner streams, and on the other hand there has been increasing production of fine mesh coal, resulting directly from adoption of the modern mining methods so essential to the economy of the coal mining industry. Cleaning fine coal with the same precision possible with coarser coals is a difficult task, and for coals finer than 200 mesh it has been impractical. Furthermore, the inclusion of -200 mesh material in the final product markedly increases costs of dewatering and thermal drying, which are necessary steps if coal is to meet market requirements. Consequently these extreme fines have generally been wasted. As a result, problems have been created in many districts because there has not been enough area for adequate settling basins.

Jan 2, 1958

By D. T. Jones

In view of the importance of the application of scientific principles to the production of oil from the reservoir, the Production Staff of the Anglo-Iranian Oil Co. (late Anglo-Persian Oil Co.) has been engaged for some years on an intensive program of research on the physical properties of crude oil. Problems involving the retention of crude oil in capillaries and fine fissures demanded for their solution a knowledge of the surface tension and specific gravity of the crude under reservoir conditions, and it is the purpose of this paper to describe briefly the methods adopted for the determination of these properties, and to present the more important results. A detailed article was published in volume 1 of the World Congress Proceedings (1933). Surface-tension observations on crude oil regassed at high pressures with natural gases have been made in the past by Beecher and Park-hurstl and Swartz2, but up to the time of the investigations in Iran no one seems to have carried out experiments with gas-saturated crude direct from the reservoir and kept at its original pressure. Results obtained in this manner are obviously of greater practical value for solving problems connected with the reservoir. Method of Measurement No apparatus for the measurements, under the pressure conditions involved, was available, and a suitable instrument had to be designed and constructed in the Fields workshops. Careful consideration of the matter led to the adoption of a method for measuring the surface tension which did not involve a knowledge of the specific gravity of the oils under the working conditions: the main reason for this being that up to that time no accurate determination of the specific gravity had been made under these conditions. The method adopted involves the measurement of the actual tension in an oil film, and is effected by means of

Jan 1, 1936

By D. T. Jones

In view of the importance of the application of scientific principles to the production of oil from the reservoir, the Production Staff of the Anglo-Iranian Oil Co. (late Anglo-Persian Oil Co.) has been engaged for some years on an intensive program of research on the physical properties of crude oil. Problems involving the retention of crude oil in capillaries and fine fissures demanded for their solution a knowledge of the surface tension and specific gravity of the crude under reservoir conditions, and it is the purpose of this paper to describe briefly the methods adopted for the determination of these properties, and to present the more important results. A detailed article was published in volume 1 of the World Congress Proceedings (1933). Surface-tension observations on crude oil regassed at high pressures with natural gases have been made in the past by Beecher and Park-hurstl and Swartz2, but up to the time of the investigations in Iran no one seems to have carried out experiments with gas-saturated crude direct from the reservoir and kept at its original pressure. Results obtained in this manner are obviously of greater practical value for solving problems connected with the reservoir. Method of Measurement No apparatus for the measurements, under the pressure conditions involved, was available, and a suitable instrument had to be designed and constructed in the Fields workshops. Careful consideration of the matter led to the adoption of a method for measuring the surface tension which did not involve a knowledge of the specific gravity of the oils under the working conditions: the main reason for this being that up to that time no accurate determination of the specific gravity had been made under these conditions. The method adopted involves the measurement of the actual tension in an oil film, and is effected by means of

Jan 1, 1936

By W. M. Pierce

THE present work has been done in an endeavor to correlate and complete the data on the constitution of alloys of zinc with other common, metals, dealing exclusively, however, with the zinc-rich alloys in which the zinc content is between 90 and 100 per cent. This investigation has included the systems lead-zinc, cadmium-zinc, iron-zinc, copper-zinc, aluminum-zinc, nickel-zinc, manganese-zinc, cobalt-zinc, tin-zinc, and magnesium-zinc. The important ternary system zinc-lead-cadmium and the zinc corners of other ternary systems have been investigated in connection with this work but will not be dealt with here. Zinc does not form a single homogenous zinc-rich solid solution over any considerable range of concentration with any of the metals mentioned. A limited range of solid solubility is said,; by previous investigators, to occur in several cases and certain effects on the properties of zinc are attributed (with varying degrees of consistency among different writers) to the presence of certain other metals dissolved in zinc. The increasing use of rolled zinc and the possibilities offered by zinc as a casting alloy in certain fields have it made essential to determine precisely these equilibrium relationships. In carrying out this .investigation reliance was placed chiefly on two methods, conductivity measurements and microscopic analysis. The first method proved valuable in determining the existence and extent of solid solubility. The second method stands alone as a means of determining structural characteristics and supplements the first method in the measurement of solid solubility. The scleroscopic hardness of all conductivity specimens was measured partly for its value from the point of view of mechanical properties and partly; as a check on the conductivity curves in indicating the limits of solid solubility. No hardness curves are included in this paper, for in no case were they important in arriving at the constitution of any system.

Jan 2, 1922

By E. M. Boatman, S. J. Pirson, R. L. Nettle

More than a decade ago some theoretically derived relationships were proposed that permitted the prediction of the relative ability of reservoir fluids (oil, gas, water) to flow simultaneously within the porous structure of rocks. While many successful predictions of fluid-flow ratios from wells have been made from electric logs, the theoretical deductions have not been subjected to laboratory verifications. For the relative permeability to liquid and gas, simultaneous flow of water and air was used, employing the familiar external-gas-drive technique. While in the process or water desaturation, the resistivities of the test cores (Woodbine sand) were measured. Their permeabilities varied from 10 to 280 md. The laboratory results indicated the need for changing the values of exponents in the theoretically derived formulas, whereas the form of the functions of resistivities and saturations remained as derived by theory. For the relative permeability to oil and water, the three-core dynamic technique was used on six cores. In this case it was found that the formulas were valid with but slight modification as derived by theory, to a sufficient degree of accuracy for engineering use and for well productivity prediction from electric logs. INTRODUCTION Conventional quantitative well log interpretation generally stops after reasonable values for formation porosities and water saturations have been established. Yet such in formation is insufficient to predict either the outcome or the desirability of well tests and completion, let alone the economic aspect of producing oil- and gas-bearing sections which might have been established by conventional log analysis. To give an engineering answer to such questions, it is necessary to predict the expected fluid flow ratios, the productivity index and the ultimate recovery from potentially productive wells. This problem requires in part for its solution a determination of the relative permeability characteristics of the potentially producing formations, both to oil (or water) and gas, and to oil and water.

Jan 1, 1965

By Edwin Shorey

IN THE southwestern Wisconsin zinc district, lying in Lafayette, Grant, and Iowa Counties, and the adjoining territory in northwestern Illinois, the orebodies are generally small, and are mined out in a few years. Many of the mines are developed with an expectation of five years or less of actual production. For this reason, as well as for considerations of economy, certain features in the development practice, which have been worked out with a view toward keeping the ratio of time required for, development to that occupied by actual production as small as possible, are of interest. ORGANIZATION The organization of a crew for, this work is as follows: Inasmuch as speed in sinking is desirable, the shaft crew comprises three shifts working 8 hr. each. In the smaller shafts, running up to 6 by 12 ft. (1.8 by 3.6 in.) in size, two men are employed on a shift; in larger shafts an additional man is usually employed. A mine foreman, or ground boss, has general control of the work of the three shifts. He is usually with the crew on the first and the early part of the second shifts, and plans the work to be done for the third shift when it comes on. His schedule, of course, is flexible and when pump changes, or other special conditions warrant, he, arranges his working time to suit the occasion. The surface crew for a sinking operation is made up of two hoistermen, each working 12-hr. shifts. Since the various operations in the shaft must be conducted in succession,. and not in combination, one with the other, separate attendance for hoisting and general plant is unnecessary. Drilling is done when no hoisting is necessary and vice versa. The hoisterman trams out and dumps the excavated material which the crew in the shaft is mucking, as a part of his regular hoisting work.

Jan 8, 1920

By Kung-Lee Wang, Brian W. Mackenzie, Warren E. Morrison, DeVerle P. Harris, George F. Sharrard

The term "mineral economics" is applied to a wide range of activities in the mineral industries. Earlier chapters have described the application of economic concepts to the mineral industries-supply, demand, conservation, tariffs, etc. The solution of mineral economics problems is often assisted by the application of quantitative methods. The purpose of this chapter is to describe a number of quantitative methods-econometric, operations research, and management science techniques-which find application in the analysis of mineral economics problems. These methods include input-output analysis, trend analysis, forecasting techniques, simulation, multivariate statistical analysis, mathematical programming, and market research techniques. The purpose of this introductory section is to provide a mineral economics framework for the application of these methods. Mineral economics is a subdivision of economics that is justified by a sufficient number of economic problems in the mineral industry requiring special experience and an unusual combination of skills. These problems are concerned with the conversion of minerals as geologic resources to minerals as economic goods. The mineral conversion process is outlined in Fig. 8.A.1. The physical occurrence of mineral deposits in nature and the market demand for mineral products in the economy provide the basic stimuli. The conversion process embodies a number of sequential stages-exploration, the development of mineral deposits, and mineral processing facilities and, consequently, productive activity to supply market demand. Changes in demand and the depletion of deposits illustrate the dynamics of the process. Mineral economics applies economic con-

Jan 1, 1976

By D. T. Peters, C. R. Cupp

Aging of commercial 18 pct Ni maraging steel and of related binary, ternary, and quaternary alloys has been studied by electrical resistivity, X-ray diffrac-tion, and hardness measurements. The aging process is in three stages: 1) recovery of martensite; 2) two precipitation reactions; 3) formation of nickel- rich austenite. The main objective of this work was to discover the nature of the Co-Mu interaction. Addition of cobalt to the Fe-18 pct Ni-5pct Mo alloy results in acceleration of the pvecipitation reaction by increasing the super-sat~lration 0f molybdenum. The cobalt-containing al- loys show no incubation period for the precipitation reaction, but the alloy without cobalt shows an initial slow reaction. These results are interpreted in terms of precipitation on dislocations. At low aging temperatures, the presence of cobalt leads to the appearance of a second type of precipitate which is a particularly effective hardener. Cobalt was found to retard the formation of austenite. Overaging is a combination of classical overaging and the formation of austenite in the structure. he- activation energy for the precipitation reaction determined from resistivity ,measurements is 42.8 kcal per mole and the growth of the precipitate is found to obey at law at high tenzperatures and a tU3 law at low temperatures. HE mechanism of strengthening of the 18 pct Ni maraging steels has been studied extensively since 1962.&apos;-? The strengthening is due to precipitation hardening of the martensitic matrix. The main precipitate is an inter metallic compound involving molybdenum, but there is disagreement about its identity.

Jan 1, 1967

By M. M. Mebta, G. W. Dean, W. H. Somerton

With the advent of underground heating operations, interest has developed in the alteration of rock properties by high-temperature treatment. In the present work a number of sandstones were heated to temperatures in the range of 400°C to 800°C under both atmospheric and simulated reservoir pressures. Pertneabilities increased by at least 50 per cent and sonic velocities and breaking strerlgths decreased by an equivalent amount. Differential thermal expansion and other reactions of constituent min-era1 grains are the causes of these alterations. INTRODUCTION In the underground combustion of petroleum reservoirs, temperatures of the order of 600C are reported to have been reached in the combustion zone.&apos; At this temperature rocks are subject to extensive thermal alteration. Temperatures of this magnitude and higher may also occur in subsurface formations when subjected to bottom-hole heating, thermal drilling operations, and underground nuclear explosions. Temperatures of this magnitude might also be generated by conventional rock drilling methods at points of bit-tooth contact. In earlier work, the permanent deformation of rocks resulting from heating was reported. Major structural damage of rocks occurs due to differential thermal expansion of mineral constituents. A number of mineral alterations including crystal inversions, loss of water of crystallization and dissociation, may also contribute to changes in physical structure and properties of rock. In the present work, samples of three typical sandstones were heated to several temperatures up to a maximum of 800C and then allowed to cool to room temperature. Heating was done under both atmospheric pressure and simulated reservoir pressure conditions. Physical properties of the samples were measured before and after heating and comparisons made. Measured properties included permeability, sonic velocity, breaking strength and fracture index. Changes in physical properties were compared to changes in mineralogical characteristics as determined by thin-section. X-ray diffraction and chemical tests. EQUIPMENT AND PROCEDURE Two outcrop sandstones (Bandera and Berea) and one sub-surface sandstone (St. Peter) were selected for the tests. These samples have a wide ranee in composition and physical properties as shown in Table 1. The first series of tests was made on 2-in. diameter by 5-in. long test specimens. Test specimens used in all later work were 3/4-in. diameter by 1 1/8-in. long, this being the specimen size required for heating at simulated reservoir pressures. After careful washing, the cores were oven dried at 100 ± 5C for a minimum of 24 hours before the tests were run. Test specimens were heated in an electric furnace at a constant rate of temperature increase of 3C per minute. When maximum temperature of the run was reached, the sample was allowed to soak for one hour. The furnace was then cooled to room temperature at the same rate of 3C per minute. The entire heating operation was designed for reproducibility without subjecting the test specimens to excessive thermal shock. For samples heated under simulated reservoir pressures, a pressure cell designed by Dean was used (Fig. 1).3 The core sample was inserted into a thin-walled (0.006 to 0.01-in.) copper cup which was then mounted in a high-pressure cell. Provisions were made for the application of internal pore pressure as well as confining pressure. Tests showed that the thin-walled copper cup closed tightly around the core and satisfactorily transmitted confining pressure to the core. The core was heated by placing the entire cell into the electric furnace. The heating program was the same as that used in the atmospheric pressure runs: tempera-ture rise of 3C per minute to maximum temperature of the test, soaking at maximum temperature for one hour, and cooling at a rate of approximately 3C per minute. The cell was designed to withstand 5,000 psi at 1,000C. However, since it was considered likely that repeated heating and cooling would in time weaken the steel, 2,000 psi at 850C was set as a working limit. In the present series of tests, the pore pressure was held constant at 750 psi and the confining pressure at 1.500 psi. The pressure source was a high-pressure nitrogen tank. The two pressures were controlled manually but are accurate well within ± 50 psi.

Jan 1, 1966

By John C. Calhoun, Raymond G. Loper

Theoretical calculations for the decline of pressure and the variation of instantaneous producing gas-oil ratio with increased cumulative production have been made for reservoir systems under various producing drawdown values and for various spacings. These variables have been included by a modification of previously Published techniques. This consists essentially of utilizing a radial system flowing gas and oil in a succession of steady state calculations. The results of the calculations do not show any variation in the predicted behavior of the internal gas drive reservoir when either the drawdown or the spacing are changed. The prediction of performance on an internal gas drive reservoir has been presented by various authors. &apos;,"&apos; These predictions are in the form of a pressure decline and an instantaneous producing gas-oil ratio as a function of cumulative oil withdrawal. In making these predictions a basic assumption has been that the saturation of the reservoir is uniform throughout at any time, or that the pressure differential imposed on the reservoir system is zero. Because of these assumptions the validity of such predictions has been questioned. Their application to actual systems, where saturations are not uniform and where producing differentials exist, has been a hazardous procedure. The authors cited have used different methods of approach to the derivation of equations for making their predictions and for arriving at a solution of both equations, but basically the same relationships are utilized in each case. In all instances the instantaneous producing gas-oil ratio is calculated from the equation: In utilizing this equation an average reservoir pressure and an average reservoir saturation must be known, the former to define ß, v, s, and uo/ug and the latter to define kg/ko. Predictions can be made, therefore, only for the conditions of a uniform reservoir saturation and a uniform reservoir pressure. This restriction of requiring a uniform oil saturation can be resolved by applying two-phase steady state flow for the radial system to the reservoir&apos;s history. Radial steady state flow is defined when the ratio of phases flowing,

Jan 1, 1949

By John C. Calhoun, Raymond G. Loper

Theoretical calculations for the decline of pressure and the variation of instantaneous producing gas-oil ratio with increased cumulative production have been made for reservoir systems under various producing drawdown values and for various spacings. These variables have been included by a modification of previously Published techniques. This consists essentially of utilizing a radial system flowing gas and oil in a succession of steady state calculations. The results of the calculations do not show any variation in the predicted behavior of the internal gas drive reservoir when either the drawdown or the spacing are changed. The prediction of performance on an internal gas drive reservoir has been presented by various authors. &apos;,"&apos; These predictions are in the form of a pressure decline and an instantaneous producing gas-oil ratio as a function of cumulative oil withdrawal. In making these predictions a basic assumption has been that the saturation of the reservoir is uniform throughout at any time, or that the pressure differential imposed on the reservoir system is zero. Because of these assumptions the validity of such predictions has been questioned. Their application to actual systems, where saturations are not uniform and where producing differentials exist, has been a hazardous procedure. The authors cited have used different methods of approach to the derivation of equations for making their predictions and for arriving at a solution of both equations, but basically the same relationships are utilized in each case. In all instances the instantaneous producing gas-oil ratio is calculated from the equation: In utilizing this equation an average reservoir pressure and an average reservoir saturation must be known, the former to define ß, v, s, and uo/ug and the latter to define kg/ko. Predictions can be made, therefore, only for the conditions of a uniform reservoir saturation and a uniform reservoir pressure. This restriction of requiring a uniform oil saturation can be resolved by applying two-phase steady state flow for the radial system to the reservoir&apos;s history. Radial steady state flow is defined when the ratio of phases flowing,

Jan 1, 1949