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By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.' Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.' The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965

By N. E. Brown, F. L. Versnyder

THE apparent dependency of the electrical characteristics of hexagonal crystalline selenium on microstructure has aroused much interest in microscopical studies of selenium. Microscopic observations on the crystallization of selenium have been made by Escoffery and Halperin,' P. H. Keck,' and other investigators. It is the purpose of this paper to discuss the microstructural changes observed on polished cross-sections of single layers of selenium after various heat treatments. Observations were also made on crystallization of the free-surface layer of these deposits. In general, all of the transformations studied were either transformations of the vitreous selenium to hexagonal selenium or micro-structural transformation of the hexagonal selenium itself. Procedure The selenium used in this work was obtained from the American Smelting and Refining Co. and was approximately 99.96 pct pure. An intentional impurity of 1 part per 2,000 of bromine was added to the material prior to evaporation. A thickness of approximately 0.002 in. of this selenium was vapor deposited on an aluminum base plate. The maximum plate temperature during the vacuum vapor deposition was 140°C. Mounting of the cross-sectional specimens for metallographic study could not be done in plastic mounting media, as is customary, since temperatures in excess of 50°C would cause unwanted transformations. Consequently, a simple clamp-type device was used to mount the specimens for preparation. All grinding operations were then done carefully by hand in order that the specimen not become heated during this operation. Wet polishing was done on the conventional metallographic polishing laps, using successively finer grinding powders. An extremely careful polish is necessary, since observation and micrography of the specimens are done in the unetched condition under polarized light. The two observations of crystallization made on the free surface of vitreous selenium deposits (Figs. 4 and 5) were made on surfaces which were perpendicular to the cross-sections studied. These free-surface layers were examined directly, i.e., no pre- vious metallographic preparation, as obtained from the vacuum vapor deposition. Microscopic Observations A study was made of polished cross-sections of the vitreous selenium as-deposited. It was noted that in all cases there was columnar crystallization adjacent to the base plate, which appeared to occur during the vacuum deposition process. This observation has also been made by Keck? It also was observed that vagrant spherulitic crystallization occurred in the vitreous selenium. The term "vagrant" is used, since these spherulitic grains appear to crystallize at random throughout the vitreous selenium during the vacuum deposition process. Columnar crystallization at the A1-Se interface and a typical spherulite observed in a polished cross-section of "as-deposited" vitreous selenium may be seen in Fig. 1. Cross-sectional samples of vitreous selenium studied after heat treating individual samples for 20 min in 10" steps from 80" to 220°C revealed that crystallization—in this case, columnar crystal growth —proceeds from the aluminum base plate to the surface of the specimen (Fig. 2). Crystallization was microscopically observed to be complete after the 130°C heat treatment. Visual examination of the free surface of the specimen after the 130 °C heat treatment revealed the readily recognizable grey appearance of the completely crystallized selenium, in corroboration of the microstructural observations. No microstructural transformations then appeared to take place between 130" and 190°C. At 190°C the beginning of recrystallization appeared and proceeded until the columnar grain structure had been completely transformed to equiaxed grains between 210" and 220°C (Fig. 3). Naturally, the grain size of the recrystallized grains at the lower temperatures (190" to 210°C) was smaller than is illustrated in Fig. 3. In addition, polished cross-sections of deposits heat treated at 140°C for 10 min to cause complete crystallization and, subsequently, heat treated in 10" steps from 80" to 220°C for 20 min were studied. As expected, no microstructural transformations took place until the beginning of recrystallization was observed at 190°C. A comparison with the previously studied specimens revealed that recrystallization proceeded almost identically in the two experiments although in the first case the deposits were vitreous prior to the series of heat treatments and in the second case they had been crystallized by a previous heat treatment. By heat treating for longer times (180 min) at lower temperatures, the

Jan 1, 1956

By Robert E. Green, P. W. Kingman

Application of a constant geometry compression test to single crystals of aluminum of selected diameters from 1/4 to 1/64 in. showed the presence of a diameter-dependmt size effect. The most pronounced effects were found in those crystals oriented for single slip, while for specimens possessing orientations in the comers of the standard stereographic triangle virtually no size effect was exhibited. The yield stress of the crystals oriented for single slip was found to increase with decrease in specimen diameter, while the strain-hardening rate was found to be lower for the smaller specimens. The experimental results are in general agreement with those of other investigators obtained from lensile tests on copper and aluminum crystals. THE earliest systematic investigation of a possible size effect on the plasticity of metals was that of no,' who in 1926 performed tensile tests on cylindrical aluminum single crystals with diameters of 3 to 8 mm. Ono concluded that the gross stress-strain curve did not show a diameter dependence, but that the resistance to slip for strains of 0.1 pet and less appeared higher for 3-mm-diam crystals than for larger sizes. Later studies of aluminum by Maddin et al2 tentatively concluded that a size effect exists, but the conclusions were again open to question because of inconsistencies in the experimental data. Wu and Smoluchowski3 had previously shown that the slip system activated in a single-crystal sheet specimen of aluminum is a function of the specimen cross section in the slip direction, but no stress-strain data were obtained. Subsequently Fleischer and Chalmers4 studied the effect of the length of the slip direction of the primary-slip system on the stress-strain curve by testing aluminum crystals with geometrically dissimilar cross sections. In the course of this investigation a size effect was indicated in rather large crystals; however, the number of these tests was small. Other investigators have indicated that a size effect in aluminum is appreciable only for diameters of 0.5 mm or less.5, 6 Size-effect studies have also been carried out on copper crystals, the most detailed being that of Suzuki et a1.7 who performed tensile tests on specimens of many diameters ranging from 2 to 0.12 mm. Suzuki found a strong size dependence in the easy-glide region, both the extent of the easy glide and the hardening rate in easy glide were size-dependent, and the size effect was found to be orientation-dependent. Suzuki's results are in agreement with the less extensive observations of Pater-sonB and those of Garstone et al.9 A size effect was found by Rebstock using tubular copper crystals.'0 Size effects have also been noted in a brass,6, 11 in cadmium,12'19 and in hexagonal crystals.14 All the previously cited works have been entirely concerned with the variation of specimen cross section. The effects of specimen length and the change of specimen geometry which results from using progressively thinner specimens while maintaining the same specimen length have been largely ignored. A theoretical discussion of the effects of specimen length and geometry has been given by Hauser and Jackson,15 who predict a grip effect on easy glide as a function of specimen geometry provided that the specimen dimensions are large compared with the spacing between the slip bands, and by Fleischer and Chalmers,18 whose analysis of grip effects resulting from lattice rotation predicts an increase in easy glide with an increase in specimen length. A study of size and geometry effects in aluminum crystals by Kitajima and shimba17 indicated increasing amounts of easy glide in specimens of increasing length and identical cross section, and nearly identical stress-strain curves for specimens of different sizes having constant length-to-diameter ratios. Since the present study is primarily concerned with diameter dependence, the following factors were taken into account: specimen material, specimen geometry, testing method, range of sizes to be tested, and possible influence of surface and volume effects. Aluminum was chosen because of the present lack of conclusive results and the seeming possibility of size effects at relatively large diameters, the

Jan 1, 1964

By H. Udin

G. KUCZYNSKI* and B. H. ALEXANDER*—This paper represents a most noteworthy attempt to evaluate experimentally the surface tension of a solid metal. Because of the great importance of such measurements, any proposed method should receive the closest scrutiny before the results can be considered reliable. In regard to the experimental method, we think that the marking of the gauge length by means of tieing knots in the wire may be the cause of some of the spread in the results. Such a knot may be expected to tighten slightly, and thus increase the gauge length, when placed under stress at high temperature. Although this effect would be very small, amounting at most to only a few times the wire diameter. A fairly tight knot in a wire will decrease the wire length by about ten times the wire diameter, thus only a slight tightening of the knot would cause considerable spread in the results. Upon plotting the stress strain curves from the authors' data, the writers found that there was a fairly consistent tendency towards an S-shaped curve, instead of a straight line. Such an effect could be caused by the tightening of the knots. The writers think, however, that the experimental results are fairly reliable, but that there may be other methods of interpreting them depending upon what mechanism is assumed to be responsible for the shrinkage of the wires. The authors have assumed that the stress due to surface tension results in viscous flow. It should be made clear that it has never been demonstrated that viscous flow can occur in metal crystals even at very high temperatures. The experiments of Chalmers13 on tin, which are so frequently quoted as giving evidence of viscous flow at low stresses are by no means satisfactory. In his experiments, Chalmers found that only the initial rate of flow was approximately proportional to stress. He also found that the rate of flow varied markedly with time which, in his experiments, was less than 2 hr. Inasmuch as there is no proof of viscous flow in metals, and the authors have brought forth no conclusive evidence on this point, it may be worth while to investigate other possible mechanisms of material transport which would account for the shrinkage of the wires. The writers wish to point out that in these experiments the shrinkage of the wires can be adequately explained, according to a self diffusion mechanism. Thus, if we assume a concentration gradient for self diffusion which is a function of the radius of curvature of the wires, and assume that diffusion will occur so that the total surface area is decreased, we find the following expression for the self diffusion coefficient: where k = Boltzmann constant r0 = initial radius of the wire T = absolute temperature ? = surface energy 8 = interatomic spacing t = time e = strain at zero applied stress Eq 19 may be used to evaluate the self diffusion coefficient of copper, using the strain measurements obtained by the authors for zero stress as obtained by extrapolating their curves for 5 rail wires. By inserting a reasonable value for the surface energy (1500 ergs per cm2) we find: -66,000 D = 5 X 10e RT [20] The activation energy is of the correct order of magnitude, but the frequency coefficient is much too high, indicating that surface diffusion may be playing an important role. This discrepancy in the action constant is much smaller than the corresponding discrepancy obtained by the authors for the viscosity coefficient. The writers by no means propose that this proves that the shrinkage of the wires is due to self diffusion but we merely wish to point out that there are explanations other than that given by the authors. In this, as in any kinetic phenomena, it is necessary to study the rate of the process before anything can be said about the mechanism. The determination of surface tension given by the authors is based upon an interpretation of the data which embody the concept of viscous flow. The final proof of this concept will be obtained only after the time relationships confirming the authors' Eq 15 have been conclusively established. The rough linearity of the stress strain curves obtained by the authors for experiments run the same length of time should not be considered as proving that viscous flow is occurring. H. UDIN (authors' reply)—All of the test specimens were annealed at 1000°C for an hour or more before preliminary measurements were made. During this anneal the wires recrystallize, and the greatest part of grain growth takes place. Also, the knots sinter at the cross-over points. This does not in itself eliminate the possibility of end errors, although it greatly decreases their probable magnitude. It is still possible that some extension occurs due to creep in shear at the sintered points. If so, this effect would be quite independent of and superimposed on the normal shrinkage or extension of the wire itself. Within the precision of the experimental results, straight lines satisfy the data as well as do any other simple curves. Until data of greater precision are obtained, it is futile to discuss any possible trends away from linearity. The disagreement between Kuczynski and Alexander's Eq 19 and our Eq 18 is one of semantics and mathematics, not mechanism of flow, since Eq 18 is based on the self-diffusion concept of viscous flow. It would be interesting to learn how the mathematics leading to Eq 19 deviates from that of Eyring and of

Jan 1, 1950

By W. W. Schmittroth, A. Y. Bethune

The commercial analysis of Special High-Grade zinc usually involves the determination of lead, iron, copper and cadmium as impurities in the base metal. Over the past 20 years, as the result of metallurgical improvements in the art of producing Special High-Grade zinc metal there has taken place a gradual exclusion of almost all extraneous elements, and the few that do remain in the final product have been virtually reduced to the vanishing point. Thousands of tons of zinc are now commercially produced annually and made available to the trade, in which impurities are present only in the order of 0.0010 per cent or less and the sum total of all impurities does not exceed 0.0025 per cent. To such zinc the term "super-purity" might well be applied without undue exaggeration. The techniques used for production control and final analysis of Special High-Grade zinc by means of emission spectra in the laboratories of the electrolytic zinc plant of the Sullivan Mining Co. are based on the premise that self-electrodes are to be preferred over all other forms for the examination of the zinc in question. Furthermore, after a survey of the literature and considerable experimental work,' it was decided that the spectrographic method of internal control, the principle of which was first announced by Gerlach,2 using a modification of the high-voltage alternating-current arc source introduced by Duffendack and Thompson,3 with the calibration of each photographic plate as recommended by Wolfe,4 would yield the most accurate and reproducible results. Self-electrodes were chosen in order to make use of one of the unique advantages inherent in spectrographic analysis; namely, the rapid and almost effortless detection of elements other than those being quantified by the analyst; or conversely, the proof that the zinc is free from such impurities if no spectral line of the suspected element appears. This fact was verified for certain elements, and will be discussed later. Carbon electrodes impregnated or packed with zinc salts chemically prepared from the zinc to be assayed were avoided for a number of reasons. First, the chemical manipulation was another time-consuming step, which increased the chances for contamination. Second, none of the common zinc salts, such as the chloride, nitrate or sulphate, yielded reproducible results under our conditions, nor did the spectral line of the impurity appear as readily in the low concentrations as when using zinc metal. Third, no commercial carbon, except the very expensive, was pure enough to use with this grade of zinc and the continued time, effort and expense incurred in the purification of carbon were not desirable. The use of special High-Grade zinc self-electrodes introduces certain complications with regard to obtaining satisfactory excitation conditions, because it seems necessary to raise the temperature

Jan 1, 1949

By Carl J. McHargue

Rods of 99.99 + pct Al which had initial orientatzons of <001>, <118>, <115>, <111>, and random were swaged at room temperature. Changes in orientation as a function of deformation were studied on axis distribution charts. The <001> orientation appeared to be relatively stable due to the inhomogeneity of the deformation process. near the <100> zone were quickly reoriented towards <001>. Orientations on the <110> zone between <118> and <115> appeared to be stable to reductions of about 50 pct, then were reoriented toward <001>. At very high reductzotzs. movement away from the <111> orientation was observed. the requirement that a circular cross section be maintained. In addition to these mechanical factors, there are grain-boundary effects in poly crystalline materials which are not yet understood. Hartmann and Macherauch conclude, for example, that multiple slip occurs for all orientations in fine-grained aluminum and copper and that the choice of operative slip systems has no simple relationship to orientation.? Many investigators have attempted to avoid problems of interpretation caused by an initial texture by treating the starting material to obtain as ran- IT has been generally accepted that the deformation texture obtained at high reductions, e.g. 90 pct, will not be noticeably affected by a prior texture; whereas, that obtained at reductions of 40 to 50 pct may be significantly influenced by the specimen history.&apos; Some recent studies, however, have been interpreted as showing that an initial texture strongly influenced the deformation textures in rods at reductions greater than 90 pct. Freda and Cullity suggested that the <001> texture in a heavily cold-worked copper rod was due to a <001> texture in the original casting. McHargue, Jetter? and Ogle concluded that the <001> component in an aluminum rod extruded at liquid nitrogen temperature was remanent from a <001> texture in the cast extrusion billet.3 Most of the published work on the effect of initial orientation on deformation textures has been for cold-rolled or compressed single crystals,4-6 The primary interest in these studies was to examine various orientations with regard to their stability under flow? thus determining the possibility of such orientations being stable end orientations. There appears to be no published studies on the effect of initial orientation on fiber textures in polycrystalline specimens. A recent study, however, is concerned with the reorientation of individual grains in polycrystalline specimens pulled in tension.? Although the reorientation of single crystals loaded in simple tension is well known, the movements in the forming of wires and rods would be expected to be different due to the circular array of radial-compressive stresses exerted by the die walls or the rolls, and to

Jan 1, 1962

By C. H. North, L. E. Lynd, W. W. Anderson, H. Sicurdson

D. R. Grantham (Institute of Mining and Metallurgy, London, England)—This paper is a very valuable contribution to our knowledge of ilmenite and its alteration products. Two aspects are not treated in the paper and further information would be valuable. How far are the alteration processes described influenced by the original composition of the ilmenite? The word gangue is used but it is not clear whether this refers to other chemical constituents in the ilmenite, e.g., magnesia, or to other minerals loose or in composite grains. Has the work described been related to specific gravities? Pure ilmenite is stated to have a specific gravity of 4.79. Some varieties range up to over 5.0, while high magnesic varieties have a specific gravity ranging to below 4.2. Alteration to hematite might lower the specific gravity and a porous texture due to the removal of iron and the formation of rutile might also lower it. As specific gravity is a quick method which often gives an approximate indication of composition, data on the above would be valuable. L. E. Lynd (authors&apos; reply)—Because of the way in which beach sand deposits were formed, it is impossible to tell exactly what the original composition of the parent ilmenites might have been. Information on the influence of original composition on the alteration processes must be derived from other sources, perhaps by comparing the alteration products formed from ilmenite in place in a variety of rock deposits, where parent ilmenite and its alteration product can be recognized. No information of this type has yet been brought to our attention. The material referred to as gangue includes all constituents other than oxides of titanium and iron. Nearly all of this was present as separate grains of garnet, augite, hornblende, quartz, feldspar, spinel, or other gangue minerals. Inclusions of gangue minerals within ore grains were rare, and we believe there is little MgO (1 pct or less) or other impurity actually held in the ilmenite structure in any of the concentrates studied. No specific gravity measurements were made on the samples studied. However, the suggestion that alteration involving loss of iron would lower the specific gravity is a very reasonable one, and is in accord with the findings of Creitz and McVay (Ref. 9 of our paper) who reported two magnetic opaque fractions from Trail Ridge, Fla., to have the following specific gravities and pompositions: The specific gravity of this porous, high TiO² alteration product of ilmenite is closer to that of rutile (4.25) than to that of ilmenite. Due to the porosity, it may even be less dense than rutile, although lower in TiO² and higher in iron.

Jan 1, 1955

While coal was undoubtedly seen by the Spanish explorers in Texas, no mention can be found of it in any of their available published records; it was likely noticed by the first Americans, and coal along the Rio Grande River was reported in 1834.1 The next record is that of brown coal in Bastrop County in 1837 by James Nicholson and Judge Pinckney Hill? Dr. Riddell saw brown coal along the Trinity River in 1839 and described it as follows: "In the banks of the Trinity, associated with the iron ore, and overlying the brown coal, whole trees and fragments of trees, piled sometimes one upon another, present themselves completely transformed into stone. In some logs a diversified metamorphosis is observable; one portion of the vegetable structure having been replaced with silex, another with brown oxide of iron, and a third is bitumenized or converted into coal. "In concern with Dr. F. B. Page, I took considerable pains in the exploration of the Trinity brown coal formation., As no excavations for working have yet been made, the best places for inspecting the formation are where the Trinity cuts its way through the highlands, or where its banks present themselves in bold high bluffs, as at New Cincinnati, and near the site of the projected town of Osceola. The coal lies in horizontal strata, dipping one foot in thirty to the northwest. The main stratum at the latter place, just above Bedias creek; is represented by the concurrent statement of W. C. Brookfield, surveyor, Mr. James S. Hunter, of Huntsville, Texas, Dr. Page, and some other persons whom I consulted, as between six and seven feet in thickness, the lower portion being between three and four feet above low water mark. Unfortunately, during my sojourn there, the river was unusually high and turbid for the season of year; I could not consequently verify the same by personal observation and measurements. The most considerable coal beds which I had opportunity fully to inspect, were in the Trinity bluffs, southwest side, at New Cincinnati, six miles lower down, and just below the mouth of Salt creek, near six miles above. The workable stratum of brown coal in each of these localities is about five feet thick, and situated some fifteen feet or so above low water mark. In quality it is said to be precisely similar to the coal in the seven feet bed."2 . Moore in 1840 mentioned coal in the vicinity of Great Salt Lake, through which the Brazos flows; lignite in Bastrop County; lignite in the banks of the Colorado River a few miles above Lagrange in Fayette County; a deposit of excellent coal in the bed of the Sabine River, 30 miles above the

Jan 1, 1942

By C. Fairhurst, A. M. Starfield

As a practicing mining engineer, I face many rock mechanics&apos; problems daily and would like to mention one or two examples to illustrate the current gap between laboratory investigations and actual field problems. I would like to endorse Dr. Obert&apos;s suggestion that more field measurements and observations should be undertaken. There is an ever-increasing body of data beginning with Hast&apos;s results in Sweden,l then measurements at Elliot Lake, Canada, and so on, including our own measurements at White Pine, which clearly indicate that the horizontal stresses underground are often at least as large as the vertical stresses. Visual obsenation of the deformation of roof and pillars (including failure due to horizontal compression) also demonstrates that the horizontal stresses are often most important. Yet almost every laboratory investigation begins with the assumption that the only stresses acting are vertical. Roof spans in layered formations. for example, are calculated on the assumption that the rock behaves as a gravity loaded beam. This is all too often unrealistic. Roof bolts are also often considered to be simply means of suspending the gravity loaded beams. As Dr. Reed has mentioned they are probably, in fact, acting to restrain a beam which is attempting to buckle due to lateral pressure. The fact that moisture can reduce the strengths of some rocks as much as 50 percent has been known for many years. In the mine me are almost always faced with wet rock, yet no one has investigated ways in which this wakening effect can be overcome. as, for example, by waterproofing the rock. C. Fairhurst, University of Minnesota I would like to mention that we have found,2 from stress-relief determinations, that appreciable (over 1000 lb per sq in.) horizontal pressures occur also at the surface in granites quarried in central Minnesota. Whilst I agree that more field measurements are desirable, it is important to point out that most university research is undertaken by graduate students who must attend classes daily. Their research is therefore restricted to the laboratory. A.M. Starfield, University of Minnesota No one denies the importance of obtaining: data from field measurements. It is equally important, however, that field measurements be guided by theory. Much time and money can be wasted by indiscriminate measurement. An example of the value of theory in interpreting measurements is given in Dr. Obert&apos;s comments on the time dependent strain observed in a salt mine. He anticipated that the stress at the wall of the opening would change with time because salt is viscoelastic rather than elastic. It can be shown from theory that if an excavation in a viscoelastic medium is unsupported, then the stress at the wall does

Jan 1, 1967

By B. G. Hurd

A liquid-Freon permeameter suitable for making routine permeability determinations on small plug samples is described. The instrument is characterized by simplicity of design and ease of operation, and can be assembled inexpensively from stock items of laboratory equipment. It combines the unique advantages of both liquid and gas permeam-eters while eliminating many undesirable features of both general classes of instruments. Precision and accuracy of the specific Freon permeability measurements compare favorably with results of conventional liquid and gas permeameters. INTRODUCTION The liquid-Freon permeameter described in this paper was designed and built for special investigations of the properties of petroleum reservoir rocks. However, its unique advantages over conventional gas and liquid permeameters make it eminently suitable for routine use in the core analysis of small plug samples. In general, gas permeameters are very popular because of their simplicity of design and ease of operation. However, apparent gas permeabilities are normally higher than true specific permeabilities unless special corrections for gas-slippage are applied. Since these corrections require two or more measurements at different internal gas pressures, much of the time advantage of the specific gas permeability measurements is lost. Liquid permeability measurements, on the other hand, require no slip correction, but liquid saturation of the sample is time-consuming and difficult to insure. Often, too, the saturating liquid must be extracted or dried from the plug before it can be used for another experiment. The liquid-Freon permeameter described herein retains the inherent accuracy of the liquid permeameter, while affording the speed and ease of operation of the gas permeameter. Freon-12 (dichlorodifluoromethane) is a haloge-nated hydrocarbon, immiscible in the liquid phase with water. It may be considered as an oil phase in laboratory fluid-flow studies. Like butane and propane, it is a gas at normal room temperatures and atmospheric pressure but can be liquefied at moderate pressures. Complete liquid saturation of a plug sample with any of these fluids can be easily achieved by condensing vapors in the sample and operating the permeameter at a pressure above the vapor pressure of the liquid. Freon-12 is superior to butane or propane for permeability measurements only in that it is relatively nontoxic and completely incombustible, and thus presents no fire or explosion hazard. Freon-12 is believed to be completely nonreactive with most petroleum-reservoir rock samples. It volatilizes immediately from a plug on depressurizing to leave a clean, dry sample suitable for subsequent experiments. Thus, the inherent risk of changing physical properties of rock samples by cleaning and drying operations between permeability measurement and subsequent experiments is eliminated. DESCRIPTION OF THE PERMEAMETER The design of the liquid Freon-permeameter is shown schematically in Fig. 1. Regulated nitrogen pressure caps are used both as a driving pressure

By Sidney A. Swensrud

The 24-in. crude-oil line. and- the 20-in. petroleum-products line, built as a war emergency by the United States Government and running from points in Texas to the New York-New Jersey-Philadelphia area, were constructed only because of the inability during the war to continue nor-inal ocean tanker movements from the Gulf Coast to the East Coast. The postwar disposition of these lines may be considered as one of the important problems of the postwar readjustments in the oil industry, if not the most important one. In the first place there appear to be many complications in keeping the lines in crude-oil or petroleum-products service. This conclusion was reached also in a study by T. E. Swigart, President of Shell Pipeline Corporation.&apos; Since the lines are too largc for any one company to utilize, and since it appears likely that a surplus rather than a deficiency of tankers will exist after the war, most companies probably will feel that they can achieve lower costs and more satisfactoiy results from the resumption of tanker movements to the East Coast rather than by endeavoring to take over or utilize the capacity in the large pipe lines under some tariff-rate structure. As for using the lines for making deliveries to the middle west or central eastern areas, it would appear that when the war is over and normal transportation arrangements can be resumed, there will be no need of any extra capacity for such deliveries. Therefore, the War Emergency lines could be utilized for this purpose only if privately owned pipe lines and other transportation facilities were to be displaced. Against this rather unprepossessing prospect for use in petroleum or product service is the fact that at or near the source of the lines lie the greatest developed gas reserves in the world, for much of which there is at present no satisfactory market outlet; and at the other end of the lines lies one of the greatest concentrations of population in the world, which is not now served by natural gas. These who have been fortunate enough to use natural gas can have little doubt of its desirability as a domestic fuel. An analysis of the market potentialities and comparison with other areas where natural gas is being distributed, and where it has displaced manufactured gas, makes it seem clear beyond question that the full capacity of both of the large-diameter lines could be fully utilized in this service, and this without creating any undue drain upon the gas reserves of the nation. On the basis of an estimated capacity of roo to 120 billion cubic feet per year, the gas that might be marketed through these lines would amount to only 3 to 4 per cent of the total con-

Jan 1, 1944

By Terkel Rosenqvist

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations

Jan 1, 1949

By E. R. Brownscombe, Francis Collins

The pressure distribution in a reservoir producing an incompressible fluid by radial flow in a horizontal structure is a simple logarithmic function&apos; used daily by reservoir engineers. The assumption of an incompressible liquid is equivalent to assuming that pressure is maintained constant at the well radius and at some external "radius of drainage," or, in other words, that the entire flow into the well passes across the external radius. In most cases a well is surrounded by other wells draining adjoining areas so that the "radius of drainage" is not a line of constant pressure with flow equal to the flow into the well but rather a contour of zero pressure gradient across which no flow occurs, production being due to the expansion of the liquid within the area. The radial flow steady state pressure distribution for this case does not seem to be extensively used despite the fact that the mathematical analysis has been given in detail&apos; and the results are simple and generally applicable. &apos;The object of this discussion is to develop this result from a physical rather than a mathematical viewpoint, thereby aiding intuition in judging circumstances to which it may be applicable. If the production rate at a well in an unsaturated reservoir is maintained constant while no flow occurs across the outer radius a steady state will soon be reached in which the flow rate or pressure gradient is constant with time at all points in the reservoir. To preserve such a condition it is necessary that the pressure decline at the same rate at all points in the reservoir, that is, the curves of pressure versus radial distance at successive times are all parallel. Then each unit volume of oil is expanding at the same rate and contributing an equal share to the production. The rate of flow q across any circle r is thus proportional to the volume of the reservoir between r and the external radius re, or q = qw (I-r2/r2e) ......(1) where q, is the production from the well and it is assumed that rw is very small compared with re. This equation can be combined with the differential form of Darcy&apos;s law for radial flow, 2phkr dp q =—— ........(2) aµß dr ( where q is not a constant as in the incompressible flow case but is a function of r given by Equation (1). If Equation (1) is substituted in Equation (2) the variables p and r can be separated and the result integrated to obtain the pressure distribution p = pw +--------In------------- 2pkh[ rw 2re2] ......(3) This equation differs from the incompressible case only in the addition of the term proportional to the square of the radius

Jan 1, 1950

By L. D. Ricketts

Discussion of the paper of L. D. RICKETTS, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 100, April, 1915, pp. 711 to 737. FREDERICK LAIST, Anaconda, Mont.-I am going to tell you of some of the results we have been getting in Anaconda during the past two or three months in a large plant which was finished in May. We commenced work in Anaconda a year and a half ago on the construction of a leaching plant which was to have a capacity of 2,000 tons per day. The plant was to treat tailings from the concentrator, containing about 12 1b. of copper to the ton. During the past year we changed our plans and decided to use the flotation process on the tailings from the concentrator, which contained no oxidized copper, and apply the leaching process only to tailings which had accumulated in a large dump below the works. This dump contains about 15,000,000 tons of tailings, and since some of the copper in it is oxidized, we felt that the application of the flotation process would result in the loss of too much of the oxidized copper, particularly as time went on. In starting up we had a number of difficulties to overcome, as is usually the case. They were not of a serious character. The results obtained, so far, have been decidedly encouraging. During July the plant treated a total of 50,000 tons of tailings, or an average of 1,610 tons per clay. The extraction was about 83 per cent., which, on material of the grade treated, meant a. tailing assaying under 0.1 per cent. copper. The acid consumption was about 65 lb. per ton, and the fuel percentage in. roasting was about 4 ¼ . We expect to cut the fuel percentage in the next month or two to about 3 per cent., the high percentage during July being clue to starting up and shutting clown furnaces. We find that iron builds up in the solution to a marked degree. This is not a serious platter with us, because we have cheap sulphuric acid and can reject solution whenever it gets too foul. The extraction of silver has been remarkably good in the large plant. It has averaged better than 75 per cent. It seems that so long as we maintain salt in the solution to a percentage of 10 per cent., the extraction is good. We allowed the salt to fall off in order to find how low a percentage we could use. At about 7 per cent. the silver extraction fell to 65 per cent. This was to be expected, because silver chloride is soluble in strong brine, but not in weak brine.

Jan 12, 1915

By John D. Gill

THIS paper assumes the incontrovertible nature of the statement that the validity of competition in the nonnatural resource industries is established firmly on the rate and extent of the economic development of the United States. It then demonstrates the nonexistence of any condition within the petroleum industry that would invalidate the principle of competition as applied to it. It points to the benefits that competition has effected in the oil industry and the reasons why the practice of the competitive principle should continue to keep the industry virile and progressive in meeting the requirements of future generations for the kind of products natural to it. Finally, it pleads for a clearer view of the affairs of the oil industry by seeing them against a background of the whole economy. INTRODUCTION Even a few years ago there would have been only an academic reason for presenting before this Institute a paper on the validity of competition in the oil industry or any other natural resource industry; today there is no more practical subject for this body to consider. In social importance it transcends attempted solutions of perplexing technical problems; and even the numerous legal and economic problems that grow out of administration of state regulatory measures appear to be of secondary importance because they would cease to exist if competition were abolished. The aspiration of certain elements of the Federal Government to acquire control of the oil industry has long been suspected The vital need for petroleum in the national defense ... confirms my belief in the urgent need of Federal legislation to safeguard our petroleum supply through prevention of waste and by establishment and maintenance of sound economic conditions in the oil industry... . But also it may be dismissed with this mere mention of it because it predicates government control and the abandonment or broad reduction of competition on a war emergency. Clearly, the fight for a nation&apos;s life may justify a government&apos;s control over men and resources that would be abhorrent and economically enervating under conditions of national security. More pertinent to the present matter, because it appears expressive neither of a personal ambition nor of an emergency condition but rather of the long-range view of a certain school of conservationists, is the pronouncement of no less an authority than the Attorney General of the United States, who has been repeatedly quoted by the press as saying that the American Petroleum Industry constituted a case "where the principle of conservation of an exhaustible and irreplaceable resource should replace the principle of competitive exploitation." The significance of this statement in the light of the commonly accepted meanings of the " principle of conservation" and of the "principle of competitive ex-

Jan 1, 1941

By L. J. Demer, W. W. Walker

AMONG several variables of the indentation hardness test is the effect of loading time on the measured hardness of a material. The most generally recommended duration of loading is 10sec.1-3 Although this short loading duration is undoubtedly satisfactory for harder metals, it is questionable that it is sufficient for very soft metals,4 or for certain plastics.5 The effect of duration of loading on the measured hardness of ionic crystals is largely unknown, although Onitsche and Mitsches found that the indentor (under a very low load) had not yet reached equilibrium after 60 sec in a variety of ionic crystals. To extend further the data of Onitsche and Mitsche, a systematic study was made of the effect of duration of loading for longer periods, up to 50,000 sec, on the 136 deg Dph of synthetic lithium fluoride. For comparison, less extensive tests were made on synthetic magnesium oxide and copper single crystals. The general procedure used was to indent a cleaved and polished (100) face of a lithium fluoride crystal using a Leitz Durimet microhardness tester. In certain cases, the indentor was so oriented as to align the diagonals of the 136 deg diamond pyramid indentation parallel to a (100) edge. In other cases the diagonal of the indentation was aligned at 45 deg to a (100) edge of the crystal. After indenting, the surface tested was etched in the acid etchant recommended by Gilman and Johnston.&apos; This revealed the position of dislocation lines which intersected the surface tested. At these points of emergence were formed the usual sharp, pyramidal etch pits as shown in Fig. 1. The specific procedure used in studying duration of loading was as follows. The surface of the crystal was indented, and the load was left on the indentor for a predetermined time. This duration of loading was varied systematically from 1 to 50,000 sec. After the desired amount of time had elapsed, the indentor was removed from the crystal and the size of the resulting indentation was determined using a micrometer eyepiece. The surface was then etched to reveal the dislocation etch pit pattern around the indentation. Procedures used for lithium fluoride, magnesium oxide, and copper were similar. Preliminary studies revealed that, although an indentation was enlarged by increasing loading time, no corresponding changes occurred in the surface etch pit pattern. Since no evidence of dislocation movement was observed on the surface, it was assumed that the plastic deformation indicated by the indentor sinking into the surface was a result of dislocation movement inside the crystal. This movement was studied bf making a series of surface indentations in a crystal corresponding to various lengths of time, cleaving the crystal vertically through the indentations, etching the freshly

Jan 1, 1964

By Sidney A. Swensrud

The 24-in. crude-oil line. and- the 20-in. petroleum-products line, built as a war emergency by the United States Government and running from points in Texas to the New York-New Jersey-Philadelphia area, were constructed only because of the inability during the war to continue nor-inal ocean tanker movements from the Gulf Coast to the East Coast. The postwar disposition of these lines may be considered as one of the important problems of the postwar readjustments in the oil industry, if not the most important one. In the first place there appear to be many complications in keeping the lines in crude-oil or petroleum-products service. This conclusion was reached also in a study by T. E. Swigart, President of Shell Pipeline Corporation.&apos; Since the lines are too largc for any one company to utilize, and since it appears likely that a surplus rather than a deficiency of tankers will exist after the war, most companies probably will feel that they can achieve lower costs and more satisfactoiy results from the resumption of tanker movements to the East Coast rather than by endeavoring to take over or utilize the capacity in the large pipe lines under some tariff-rate structure. As for using the lines for making deliveries to the middle west or central eastern areas, it would appear that when the war is over and normal transportation arrangements can be resumed, there will be no need of any extra capacity for such deliveries. Therefore, the War Emergency lines could be utilized for this purpose only if privately owned pipe lines and other transportation facilities were to be displaced. Against this rather unprepossessing prospect for use in petroleum or product service is the fact that at or near the source of the lines lie the greatest developed gas reserves in the world, for much of which there is at present no satisfactory market outlet; and at the other end of the lines lies one of the greatest concentrations of population in the world, which is not now served by natural gas. These who have been fortunate enough to use natural gas can have little doubt of its desirability as a domestic fuel. An analysis of the market potentialities and comparison with other areas where natural gas is being distributed, and where it has displaced manufactured gas, makes it seem clear beyond question that the full capacity of both of the large-diameter lines could be fully utilized in this service, and this without creating any undue drain upon the gas reserves of the nation. On the basis of an estimated capacity of roo to 120 billion cubic feet per year, the gas that might be marketed through these lines would amount to only 3 to 4 per cent of the total con-

Jan 1, 1944

By Terkel Rosenqvist

Few subjects in iron metallurgy and steelmaking have caused so much discussion and have resulted in so many divergent and partly contradictory statements as the theory of the distribution of sulphur between molten iron and slag. An interesting survey of the different points of view is given by Grant and Chipman.1 Grant and Chipman themselves conclude in their paper that, at least in the open hearth and electric steel furnaces, the governing reaction is a simple distribution like: FeS steel ? FeS alas [Ia] and MnS steel ? MnS alas [Ib] They conclude that no significant reaction takes place according to the more classical scheme: FeS steel + CaO slag ? FeOslag + CaS slag [2a] This is the reaction which is regarded by most investigators as the primary sulphur reaction in the blast furnaces, where it is accompanied by the reaction with carbon: FeO slag + C ? Fe + CO [2b] The writer suggests an alternative to the reactions mentioned above. It is the opinion of the writer that the a priori assumption of defined molecular compounds being present in molten steel as well as in molten slag, has retarded rather than promoted a solution of the sulphur problem. As for the constituents of molten steel, it is taking too much for granted to mention the presence of FeS and MnS. If this infers that the melt contains diatomic molecules, the statement must be made that at least such molecules do not exist in the solid state at room temperature. Solid FeS crystallizes in the nickel-arsenide structure, and MnS (high temperature form) in the sodium-chloride structure. In these structures the sulphur is surrounded by six metal neighbors, and no molecular groups can be isolated. When sulphur is dissolved in molten steel, it is expected to maintain the same coordination number as in the solid state. We know that sulphur in steel has a certain chemical potential and a chemical activity which can be expressed by the reaction: S steel + H2 ? H2S where the activity A. is proportional to the ratio PH2S/Ph2. We know also that this activity is influenced by the presence of other constituents. For instance, there is reason to assume that carbon and silicon increase the sulphur activity and manganese decreases it. However, the exact relationship here is scarcely known, and further investigations are needed. Concerning the molten slags, if anything should be assumed a priori it would be that they are composed of ionic rather than molecular parts. There are indications of this in that solid silicates form ionic structures, and molten slags show high electric conductivity and can be electrolyzed.2 It has been claimed by Taylor and Chipman3 that their activity investigations

Jan 1, 1949

By Virgil Miller, F. B. Petermann, S. F. Ravitz

The Cle Elum nickeliferous iron deposit is in Kittitas County, Washington, in a rugged, mountainous region about 23 miles north of the town of Cle Elum. The Biewett Pass deposit, which is similar in character and occurrence, is in Chelan County, about 18 miles east of the Cle Elum deposit. A more or less continuous ore zone may extend between the two deposits, since iron ore is reported to have been discovered at Iron Mountain, which lies directly between them. The ore probably was formed by meta-morphism of laterite resulting from Ieach-ing of serpentine derived from peridotite. It consists largely of magnetite grains distributed through a matrix of limonitic material containing a small amount of hematite and chromite. Many of the chromite grains have shells and inclusions of magnetite. The magnetite grains range in size from 1200-mesh to 1/4-in., the average size being 48 to 65-mesh; the chromite grains range from 20 to 150-mesh. The gangue minerals are olivine and serpentine with a small, amount of chlorite, and appear both as very thin bands in the ore and &apos;s minute fragments in the limonitic matrix. The nickel is present as minUte inclusions of a nickel silicate mineral within the magnetite and gangue par- ticles, varying in size from 1500 to about 280-mesh. Detailed analyses of 3000-lb. lots of Cle Elum and Blewett Pass ore are given in Table I. TABLE i.—Analyses of Ore Samples Per Cent Ore from Constituent cle Elum&apos; Blewett Pass Cr....................... 2.23 2-12 Ni...................... 1.43 0.9s Fe...................... 52.9 41.4 SiOz.................... 5.6 13.4 CaO.................... 0.3 0.8 MgO................... 4-1 7-5 AI2O3................... 7.0 2.g P...................... 0.022 0.034 S....................... O.O1 o.oa Mn..................... I.I 0.4 Ba..................... nil co..................... o.oa 0.02 CU..................... 0.02 0.03 As...................... 0.03 Au..................... nil Ag°..................... O.58 Pt...................... ml Fe++.................... 8.9 5-9 Fe+++.................. 44-0 35-5 « Ounces per ton, 1 sr,cte,so,","&&$ally absent: B, W, M~, T~, V, ~i, Bi, Pb. Sb. Sn. Be, In, Hg. Zn, Zr. Cd. Preliminary Tests Attempts to beneficiate the ore by ore-dressing methods, including various &apos;cornbinations of sink and float, tabling, jigging, flotation, and magnetic separation, were consistently unsuccessful. A wide variety of roasting and leaching tests were made on both raw and reduced ore, but in most of the tests little or no nickel was extracted, and in none did the extraction exceed 50 Per cent. No nickel could be volatilized as the carbonyl. by treating reduced ore with carbon monoxide. Fairly good sepa-

Jan 1, 1944

Discussion of the paper of LAWRENCE ADDICKS, presented at the Salt Lake meet-ing, August, 1914, and printed in Bulletin No. 91, July, 1914, pp. 1671 to 1674. JAMES H. PAYNE, Baltimore, Md. (communication to the Secretary*). -Mr. Addicks&apos;s account of the behavior of the nodulizer at Chrome on blast-furnace flue dust leads me to outline what has been done so far upon the application .of the same apparatus to fine sulphide concentrates. As Mr. Addicks states in his paper, the conditions prevailing in the test kiln at Yorktown in the demonstration I made for him upon Chrome material were strongly oxidizing; so much so that the sulphur was roasted down to less than 1 per cent. It is therefore to be expected that the first test made upon sulphide ore a short time after this, in which Ducktown green ore fines were used, did not show very promising results. Although the Ducktown ore contained only 13.52 per cent. of sulphur its gangue was quite fusible, and the intense heat generated by the oxidation of. the extremely fine sulphide particles slagged the mass, bringing about a condition approximating that of a Brückner roaster in distress. During the spring and summer of 1912, the writer kept working upon different schemes to cut clown this slagging. Two successful methods were finally worked &apos;out embodying opposite principles, one promoting oxidation of the finer particles and the other retarding. their oxidation. In the early part of the present year the writer succeeded in interesting the Braden Copper Co. in nodulizing, with the result that an extensive series of tests were made at Yorktown upon oil-floated concentrates covering quite a wide range in analysis. These tests led to trials in the Chrome rotary on the part of the U. S. Metals Refining Co. of Minerals Separation concentrates which they had in stock, and later to test runs to check up the Yorktown runs on Braden concentrates. The large-scale tests checked up with the Yorktown tests in every way (except fuel consumption, which was, however, correctly predicted), and led to the Braden company&apos;s decision to adopt the process at Braden. The fuel consumption upon oil-floated concentrates is not over 6 gal. per ton and in many cases is less. The action in the furnace is independent of the sulphur content, and there is actually less tendency to form nose rings in the Chrome rotary than upon flue dust. It is believed that the improvements entering into the design of the Braden kilns will cut down the nose-ring trouble to where it will no longer be a drawback to the process.

Jan 11, 1914