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By John Chipman

The concentration of a solute in a dilute ),zetallic solution may be measured by any of several parame- ters including weight percent, atom fraction, atom ratio, and lattice ratio. The ratio of filled to unfilled interstitial sites is useful for interstitial solutes. A variable 2 proportional to this ratio is used as a measuve of concentration. For component 2 irz a bitzary solution z2 = n2/Ym - nz/b) where b is the numberber of interstitial sites per lattice atom. For a t~lul-ticortzporzent solution this becomes zz = n2/(nl + Cvjnj) in which Vj = - l/b for an interstial solute and +1 for a substitulional solute. In the infinitely dilute solution the activity of an interstitial solute 2 is proportional lo z2. At finile concentration the departure from this limiting law is expressed us an activity coefficient, his coefficient is a function of concentra1io)z expressed as tevactiolz coeffcient 8; is analogous to the jark~iliar e£ bul is found to be independent of concentvation in certain solutions for which data are available. It is found that the same equations may be used to express the activity of a nonmetallic solute, sulfur, in liquid solutions of iron containing other solutes, both metallic and nonmetallic. For a nonmetallic solute or for one which strongly increases the actiuity of sulfur, it is convenient to assign arbitvarily a value vj = — 1. When this is done the derivative is found to be constant in each of the ternary solutions studied. The activity coefficient of sulfur in a complex liquid iron solution may be expressed as where nk is a second-order cross product determined in the quaternary solution Fe-S-j-k. The equation is used to calculate tlze activity of sulfur i)z three sevetl- component solutions. IN thermodynamic calculations concerning dilute solutions it is unnecessary to invoke laws and relations which extend across the concentration range to include concentrated solutions. In most binary metallic systems, as arkeen&apos; has recently pointed out, there exist two terminal composition regions of relatively simple behavior, connected by a central region of much greater complexity. When the solute is a nonmetal there is only one such region and in many systems the concentration range is extremely limited. It is the purpose of this paper to suggest a method for the calculation of activities in such a terminal region in which one or more solutes are dissolved in a single solvent of predominantly high concentration. HENRY&apos;S LAW In the usual textbook statement of Henry&apos;s law, concentration is stated in mole fraction. This has the advantage that it makes Henry&apos;s law thermodynamically consistent with Raoult&apos;s law. Since all measures of concentration at infinite dilution are related by simple proportion it follows that mole fraction, molality, atom ratio, weight percent, or any other unit of concentration can be used with the appropriate constant. At finite concentrations, however, calculations based on the law depend upon the unit employed. Deviations from Henry&apos;s law at finite concentrations depend upon the composition variable employed. They are evaluated in terms of activity and interaction coefficients2 which have become familiar features of metallurgical thermodynamics. It is the purpose of this paper to propose a measure of concentration for metallic solutions containing interstitial or nonmetallic solutes by means of which the calculation of activities in complex solutions may be simplified. The discussion will be restricted to free-energy interaction coefficients3 typified by Wagner&apos;s c|a BINARY SOLUTIONS The several measures of concentration which are to be considered are shown in line a of Table I. The corresponding activity coefficients are in line b and the deviation coefficients, sometimes called self-interaction coefficients, are in line c. Henry&apos;s law simply states that the activity coefficient approaches a constant value at infinite dilution. By adoptihg the infinitely dilute solution as the reference state and defining the "Henrian" activity as equal to the concentration in this state, the activity coefficient is always unity at infinite dilution. This convention is far sim~ler and more useful in dilute solution than emploiment of the &apos;Raoultian" activities and it will be used in the following discussion. The several definitions and equations of Table I will be referred to by means of their coordinates in the table. Early observations of deviations from Henry&apos;s law in metallic solutions were shown graphically4 rather than analytically. For the case of sulfur in liquid iron5 the slope of a plot of logfs vs (%S) was constant in the range 0 to 4.8 pct S, indicating constancy of eh2&apos; in Ic. He was proposed by wagnerz and has been widely adopted. The a function of IIIc recently employed by ~arkenl was designed specifically for dilute solutions. Darken has shown that the value of a12 remains essentially constant for many binary solutions within a substantial range of compositions. The atom ratio is directly proportional to the molalitv.<, a conventional measure of concentration. IVb and C served as the basis for smith&apos;s6 classic studies of

Jan 1, 1968

By Frank C. Kelton

It is perhaps not widely realized that extraction and saturation processes carried out on oil well core samples alter the properties of these samples to varying degrees. On the other hand it is felt by some that quick-freezing of core samples increases their permeability and porosity significantly. Accordingly, laboratory tests were carried out on 49 pairs of horizontally adjacent samples in order to differentiate between the effect of quick-freezing per se on permeability and porosity of the samples, as distinguished from the effect of the identical saturation treatment on permeability and porosity of the companion samples. Also, additional field data were obtained on comparison of frozen vs unfrozen companion samples. LABORATORY INVESTIGATION OF FREEZING us SATURATION EFFECTS Procedure The samples used in these tests were two-cm cubes cut in horizontally adjacent pairs from cores from eight Gulf Coast and Mid-Continent wells, which cores had not previously been frozen. These samples were extracted with carbon tetrachloride, dried, and air permeabilities run in the conventional manner. They were then evacuated and saturated with brine of 25,000 ppm sodium chloride content, and porosities determined by gain in weight. The samples were partially desaturated by evaporation down to an average brine saturation of 68 per cent. One sample from each pair was quick-frozen by covering with dry ice after wrapping in a single layer of paper, and allowed to remain frozen for about two hours; the companion sample from each pair was not frozen. After thawing the frozen sample, all samples were immersed in tap water overnight in order to leach out most of the brine. Air permeabilities were re-run, and the samples were again saturated with brine to determine a second porosity value. For purposes of averaging of data, the samples were grouped according to four permeability ranges, from 0 to 10, 10 to 100, 100 to 1,000, and 1,000 to 3,840 md. Average permeability and porosity changes for the frozen vs the unfrozen adjacent samples are shown in Table 1. Discussion As may be seen from Table 1, the averages of the per cent permeability increases for the quick-frozen samples ranged from 3.8 to 12.9 per cent among the four permeability groups. The average changes among the four groups of unfrozen companion samples ranged from a decrease of 0.2 per cent to an increase of 9.3 per cent. There was no particular correlation of these changes with magnitude of permeability; however, the increase for each group of frozen samples paralleled the increase for the corresponding unfrozen samples. The differences between the two sets of values are believed to be a valid indication of the effect of the quick-freezing in itself, since the treatment of the two samples in each pair was identical except for freezing. The permeability changes which are strictly the result of the quick-freezing are shown in the sixth column of Table 1. These range from a decrease of 0.9 per cent to an increase of 4.0 per cent; the overall weighted average is 1.2 per cent, as compared to an average increase of 6.8 per cent caused by the saturation treatment of the samples not frozen. The average porosity changes are in general smaller than the changes in permeability, and range from a decrease of 2.3 per cent to an increase of 3.3 per cent. The overall weighted average change ascribed to the quick-freezing is 1.0 per cent of porosity. Many factors can contribute to the changes in permeability and porosity observed when subjecting cores to the simple processes used in these tests. Such are: hydration and swelling of clay, adsorption of ions, changes in surface structure and wettability, expansion and compression effects due to ice formation, shrinking and cracking, leaching of salts and colloids, displacement of particles resulting in either blocking or enlarging of pore openings. Whatever particular mechanisms are involved. however, it is apparent not only from this study but also from other investigations in the literature&apos; not directly concerned with quick-freezing, that the effects produced by commonly used extraction, saturation and drying techniques may be of considerable magnitude The results of this study indicate that for the particular samples and techniques used, such effects are of the order of five to six times the effect of quick-freezing. insofar as changes in permeability are concerned. It may be argued that these samples might not include extremely shaly material where the effect of freezing upon permeability may be much greater. However, had such material been available for these tests, it would undoubtedly have been very susceptible also to alteration by the extraction and saturation treatment used. To investigate this point further, the individual sample data were re-grouped according to the magnitude of the average per cent permeability increases for the pairs of samples, irrespective of permeability. The results

Jan 1, 1953

By Michel Dupuy, Daniel Calais

The study of self-diffusion of plutonium in E phase has been carried out by the welded couples method. The tracer used was puZ4O which is detected by its X-ray emission (conversion lines of uranium which are computed between 13 and 21 kev). Intensities were measured with a scintillation counter. Each layer was removed in a direction parallel to the original interface with a grinding machine and a thickness measured with a pneumatic comparator. The concentration-penetration curves obtained were corrected for the effect of heating time from room temperature to annealing temperature and for the expansion due to phase transformations of plutonium. They were analyzed by the generalized Gruzin method. Self-diffusion of plutonium in E Phase is very fast cm per sec between 500" and 620°C) and the diffusion zones are 2 to 3 mm wide for annealing times ranging from 30 min up to 10 hr. The Arrhenius law gives the temperature dependence in the form: From the point of view of self-dqfusion, PUE phase falls into the anomalous bcc metals category (Tip , Hfp, Zrp, Uy) with a low-frequency factor and an activation energy lower than those provided by standard correlations. No theory proposed hitherto to explain these anomalies (influence of dislocations, of extrinsic vacancies bonded to inlpurities, of bi-vacancies) can clearly explain the self-diffusion coeffzcients of plutonium. DIFFUSION in bcc metals is a present-day problem. A recent symposium (Gatlinburg, 1964), followed by a book,&apos; has been devoted to it. A great many experiments seem to show that diffusion in certain bcc metals obeys unexpected laws. The activation energies measured are sometimes strangely low (B hafnium, y uranium). For certain metals (0 zirconium, p titanium) the curves of log D (D = diffusion coefficient) as a function of 1/T (T = absolute temperature) are not linear. The frequency factors Do, which are of the order of 1 sq cm sec-&apos; in fcc metals, vary from 1 to 10~6 sq cm sec-&apos;. Various theories have been put forward to explain these anomalies; none is yet satisfactory. We wished to introduce a new experimental result by studying the self-diffusion in c plutonium. This allotropic phase, stable from 475°C up to the melting point (640°C), is in fact bcc. Unfortunately, nothing is known of the characteristics of the point defects in this phase, which limits the scope of the hypothesis which can be made about the mechanism(s) of self-diffusion in plutonium. 1) EXPERIMENTAL METHODS 1) Principle. We used the welded couple method. The two pellets of the couple initially have different 240 isotope contents (X emitter). After diffusion, the concentration/penetration curves are drawn up by the generalized Gruzin method. 2) Gamma Spectrography. The metal used in our study is plutonium, either low in puZ4O (isotopic content 1 pct) or high in puZ4O (8 pct). The latter also contains plutonium 241 (-1 pct) and 300 ppm of ameri-cium produced by the reaction Pu2U-AmM1 + 8-. The emission spectra of these two plutoniums placed in leak-tight vinyl bags have been studied by y spectrograph~. The detector is a thin crystal of thallium-doped sodium iodide. The activity of the plutonium rich in 240 is about twice that of the plutonium low in 240 in the energy band of 17 kev (L conversion lines of uranium); this band was used in these measurements. 3) Preparation and Examination of the Diffusion Couples. Diffusion couples were made from plutonium with a high and low PU"&apos; content. Pellets (6 6 mm. thickness 3 mm) mounted on a polishing disc with ground parallel faces were polished mechanically on both sides. In this way, pellets with two parallel faces were easily obtained. The polished pellets were joined by a 6 phase anneal (420°C, 1 hr) in a small screw press (pressure of 20 kg per sq mm cold); a centering ring enabled the two pellets to be pressed coaxially. The couples then were subjected to the diffusion treatment by annealing in the E phase in sealed silica ampules in argon at atmospheric pressure. The annealing temperatures and times are given in Table I. The couples were encased in a mild steel ring, the joint interface being thus parallel to the ground face of the ring. The diffusion couple/ring assembly underwent successive abrasions by means of a magnetic plate grinder. The thickness of the abraded layer was measured with a Solex pneumatic comparator when it was less than 0.1 mm (accuracy 0.2 p) or with a mechanical micrometer (accuracy 3 p) for passes of the order of 0.2 mm. All these operations were done in glove boxes, as plutonium is particularly toxic. After each abrasion we determined the emission spectrum of the ground face. The emissive surface is defined by means of a diaphragm 3 mm in diam. We noted more particularly the X activity in the 17-kev

Jan 1, 1969

By Francis Collins, E. R. Brownscombe

A study has been made of the material balance-fluid flow method of estimating reserves and degree of water drive from pressure and production history data. By considering the effect of random pressure errors it is shown that in a particular example a standard deviation of three and one-half pounds in each of ten pressure survey? permits the determination of the reserves with a standard deviation of 8 per cent and the water drive with a standard deviation of 15 per cent, assuming that certain basic geologic data are correct. It is believed that this method of estimating reserves and water drive is useful and reliable in a number of cases. The method is particularly valuable when reservoir pressure data are accurate within a very few pounds, but may also be applied with less accurate pressure data if a relatively large reservoir pressure decline occurs early in the life of the field, as for example in an under-saturated oil field. INTRODUCTION A knowledge of the magnitude of reserves and degree of water drive present in any newly discovered petroleum reservoir is necessary to early application of proper production practices. A number of investigators have contributed to methods of relating reserves, degree of water drive, and production and pressure history. 1-8 Three types of problems of increasing complexity may be mentioned. If a reservoir is known to have no water drive. and if the ratio of the volume of the reservoir occupied by gas to the volume of the reservoir occupied by oil (which ratio permits fixing the overall compressibility of the reservoir) is known, then only one further extensive reservoir property remains to be determined, namely the magnitude of the reserves. A straightforward application of material balance considerations will permit this determination. The problem becomes very much more difficult if we wish to determine not only the magnitude of the reserves but also the magnitude of water drive, if any, which is present. In principle, a combination of material balance and fluid flow considerations will permit this evaluation. Finally, if neither the magnitude of reserves, the degree of water drive, nor the ratio of oil to gas present in the reservoir is known and it is desired to determine all three of these variables, the problem could in principle be solved by a fluid flow-material balance analysis which determines the overall compressibility of the reservoir at various points in its history. The change in compressibility with pressure would provide a means of determining the ratio of gas to liquid present, since the compressibilities of gas and liquid vary differently with pressure variation. However, in practice this problem is probably so difficult as to defy solution in terms of basic data precision apt to be available.&apos; It is the purpose of this discussion to illustrate the second case, which involves the determination of two unknown variables, single phase reserves and degree of water drive, from pressure and production history and fluid property data, and to study the precision with which these unknowns can be determined in this manner in a particular case. Although an electric analyzer developed by Bruce as used in making the calculations to be described, numerical methods necessary in carrying out the process have been devised and have been applied for this purpose. Schilthuis,&apos; for example, developed a comprehensive equation for the material balance in a reservoir. He combined this with a simplified water drive equation, assuming that the ratio of free gas to oil was fixed by geological data and that a period of constant pressure operation at constant rate of production was available to determine the constant for his water drive equation. On this basis he was able to compute the reserves and predict the future pressure history of the reservoir. Hurst developed a generalized equation permitting the calculation of the water drive by unsteady state expansion from a finite aquifer. He showed in a specific case how the water influx calculated by his equation, using basic geologic and reservoir data to fix the constants, matched the water influx required by material balance considerations. Old3 illustrated the simultaneous use of Schilthuis&apos; material balance equation and Hurst&apos;s fluid flow equation for the determination of the magnitude of reserves and a water drive parameter from pressure and production history. He used this method to calculate the future pressure history of the reservoir under assumed operating conditions. As a basis for determining reserves, Old assumed a value for his water drive parameter and calculated a set of values for the reserves, using the initial reservoir pressure and each successive measured pressure. The sum of the absolute values of the deviations of the resulting reserve numbers from their mean value was taken as a criterion of the closeness of fit to the experimental data possible with the water drive parameter assumed. New values of the water drive parameter were then assumed and new sets of the reserves calculated until a set of reserves numbers having a minimum deviation from the average was established. The average value of- the re-

Jan 1, 1949

By E. R. Brownscombe, Francis Collins

A study has been made of the material balance-fluid flow method of estimating reserves and degree of water drive from pressure and production history data. By considering the effect of random pressure errors it is shown that in a particular example a standard deviation of three and one-half pounds in each of ten pressure survey? permits the determination of the reserves with a standard deviation of 8 per cent and the water drive with a standard deviation of 15 per cent, assuming that certain basic geologic data are correct. It is believed that this method of estimating reserves and water drive is useful and reliable in a number of cases. The method is particularly valuable when reservoir pressure data are accurate within a very few pounds, but may also be applied with less accurate pressure data if a relatively large reservoir pressure decline occurs early in the life of the field, as for example in an under-saturated oil field. INTRODUCTION A knowledge of the magnitude of reserves and degree of water drive present in any newly discovered petroleum reservoir is necessary to early application of proper production practices. A number of investigators have contributed to methods of relating reserves, degree of water drive, and production and pressure history. 1-8 Three types of problems of increasing complexity may be mentioned. If a reservoir is known to have no water drive. and if the ratio of the volume of the reservoir occupied by gas to the volume of the reservoir occupied by oil (which ratio permits fixing the overall compressibility of the reservoir) is known, then only one further extensive reservoir property remains to be determined, namely the magnitude of the reserves. A straightforward application of material balance considerations will permit this determination. The problem becomes very much more difficult if we wish to determine not only the magnitude of the reserves but also the magnitude of water drive, if any, which is present. In principle, a combination of material balance and fluid flow considerations will permit this evaluation. Finally, if neither the magnitude of reserves, the degree of water drive, nor the ratio of oil to gas present in the reservoir is known and it is desired to determine all three of these variables, the problem could in principle be solved by a fluid flow-material balance analysis which determines the overall compressibility of the reservoir at various points in its history. The change in compressibility with pressure would provide a means of determining the ratio of gas to liquid present, since the compressibilities of gas and liquid vary differently with pressure variation. However, in practice this problem is probably so difficult as to defy solution in terms of basic data precision apt to be available.&apos; It is the purpose of this discussion to illustrate the second case, which involves the determination of two unknown variables, single phase reserves and degree of water drive, from pressure and production history and fluid property data, and to study the precision with which these unknowns can be determined in this manner in a particular case. Although an electric analyzer developed by Bruce as used in making the calculations to be described, numerical methods necessary in carrying out the process have been devised and have been applied for this purpose. Schilthuis,&apos; for example, developed a comprehensive equation for the material balance in a reservoir. He combined this with a simplified water drive equation, assuming that the ratio of free gas to oil was fixed by geological data and that a period of constant pressure operation at constant rate of production was available to determine the constant for his water drive equation. On this basis he was able to compute the reserves and predict the future pressure history of the reservoir. Hurst developed a generalized equation permitting the calculation of the water drive by unsteady state expansion from a finite aquifer. He showed in a specific case how the water influx calculated by his equation, using basic geologic and reservoir data to fix the constants, matched the water influx required by material balance considerations. Old3 illustrated the simultaneous use of Schilthuis&apos; material balance equation and Hurst&apos;s fluid flow equation for the determination of the magnitude of reserves and a water drive parameter from pressure and production history. He used this method to calculate the future pressure history of the reservoir under assumed operating conditions. As a basis for determining reserves, Old assumed a value for his water drive parameter and calculated a set of values for the reserves, using the initial reservoir pressure and each successive measured pressure. The sum of the absolute values of the deviations of the resulting reserve numbers from their mean value was taken as a criterion of the closeness of fit to the experimental data possible with the water drive parameter assumed. New values of the water drive parameter were then assumed and new sets of the reserves calculated until a set of reserves numbers having a minimum deviation from the average was established. The average value of- the re-

Jan 1, 1949

By R. D. Daniels, T. G. Oakwood

A study was made of the effects of small quantities of hydrogen on the mechanical properties of colum-bium. Tensile specimens, hydrogenated to concentrations of 20 to 200 ppm, were tested at temperatures of 300°, 191°, and 77°K. Although hydrogen was found to have little effect on the strength of columbium, the ductility of Cb-H alloys was found to be quite sensitive to both hydrogen concentration and temperature. At 300°K, an abrupt loss in ductility occurred at a critical hydrogen concentration, although some ductility was observed beyond the tolerance limit. A similar result was found at a lower hydrogen concentration at 191°K. At 77°K, however, a more gradual loss in ductility with increasing hydrogen concentration was observed. Hydrogenated columbium was thus observed to undergo a ductile-brittle-ductile transition. Metallographic examination of fractured specimens revealed extensive porosity at both 77° and300°K which was a distinct function of hydrogen content. At 191°K, although some secondary cracking was noted, the amount of observed porosity was minimal. These observations are interpreted in terms of hydrogen solubility and mobility as a function of temperature and in the role of hydrogen in promoting growth of microcracks. lHE effect of hydrogen on the mechanical properties of the refractory metals is not, at present, completely understood. A number of studies have shown these materials to be susceptible to hydrogen embrittlement. Roberts and Rogers1 have found that vanadium can be embrittled by hydrogen. It was further demonstrated that fracture undergoes a ductile-brittle-ductile transition as the temperature is lowered from 150° to -196°C; i.e., there is a ductility minimum observed at a certain temperature. The ductility is increased by either raising or lowering the temperature from this point. A more complete study by Eustice and Carlson2 on vanadium containing 10 to 800 ppm placed the ductility minimum at about -100°C with variations reportedly due to hydrogen content and strain rate. Ductility minima have also been found at certain temperatures for tantalum containing 7 ppm H3 and 140 ppm H.4 At hydrogen concentrations above 270 ppm, however, the ductility return at low temperatures was considerably reduced.4 In the case of columbium, some disagreement exists in the literature. Eustice and Carlson,5 Wilcox et al.,6 and Imgram et al.4 failed to find a ductility minimum although a composition-dependent ductile-brittle transition was observed. Hydrogen concentrations in these investigations were 20 ppm,5 1 to 30 ppm,6 and 200 to 390 ppm.4 However, Wood and Daniels7 observed a rather pronounced ductility minimum at hydrogen contents ranging from 19 to 252 ppm. Those theories of hydrogen embrittlement involving the precipitation of diatomic hydrogen which have been applies to ferrous metals8-12 do not seem to be applicable to the case of columbium and other exothermic occluders. Such theories propose that extensive crack formation and propagation occurs by the precipitation and expansion of diatomic hydrogen at internal voids and microcracks. However, photomicrographs of hydrogenated columbium do not show any evidence of damage introduced by the sorption and precipitation of diatomic hydrogen; rather, at high hydrogen concentrations, a hydrogen-rich second phase is precipitated.13&apos;14 In addition, a number of these theories require the development of high hydrogen pressures at voids in the structure.8&apos;10&apos;12 This does not appear to be feasible in the concentration ranges discussed in the aforementioned paragraphs. The possible interaction of atomic hydrogen with microcracks resulting from dislocation pile-ups15,16 remains in doubt since pile-ups have not been observed in bcc metals17 including columbium.18 Wood and Daniels7 have put forth the possibility that a hydride precipitation could be responsible for crack nucleation in columbium. Work by Longson19 has shown that hydrogen embrittlement of columbium parallels the bulk solubility limit; i.e., as the solubility increases, for instance with temperature, the amount of hydrogen necessary to cause embrittlement also increases. Although a hydride precipitation appears attractive as a means of nucleating microcracks in columbium, what require more intensive study are the low-temperature anomalies which have been observed, i.e., the ductile-brittle-d&apos;ictile transition characteristics. Also, the hydrogen concentrations where embrittlement occurs are often below the bulk solubility limits determined by Albrecht et al.13,14 and Walter and Chandler.20 This work is an attempt to determine more definitively the effects of concentration and temperature on the mechanical properties of dilute Cb-H alloys. EXPERIMENTAL PROCEDURE Ultrahigh-purity columbium rods, obtained from the Wah Chang Corp., were cold-reduced by rotary swaging. A chemical analysis is given in Table I. The material was cut into cylindrical blanks 1.50 ±0.005 in. long. Individual specimens were either given a stress relief anneal at 750°C or recrystal-lized at 1200°C. Resulting microstructures were either a "bamboo" structure characteristic of a wrought material or a recrystallized structure with a grain diameter of approximately 100 n. All heat treatments were carried out in a vacuum of 10-5 Torr or less.

Jan 1, 1969

By Benny J. Nelson

AS a part of the fundamental research program of Aluminum Research Laboratories, some data were obtained on the ternary system Mg-Al-Mn. As very little information on the magnesium corner of this diagram has heretofore been published, it seems desirable to make available the values found for the liquidus and solidus surfaces of this system. Procedure The settling procedure was used for the determination of the liquidus compositions. Metallo-graphic examination of quenched samples, and stress-rupture upon incipient melting, were used for the solidus determinations. The settling procedure has been described in a previous paper.&apos; Briefly, this method involved saturating the alloy with manganese at a temperature substantially above that at which the sohbility was to be determined, then cooling the melt to the latter temperature, and holding it at that temperature for a substantial period of time. Samples for analysis .were carefully ladled from the upper portion of the melt at hourly intervals during the holding period. After the ladling of each sample, the melt was stirred to redistribute some of the manganese that had already settled, because it appeared that when the latter particles of manganese again settled, they aided in carrying down more of the manganese and thus hastened the attainment of equilibrium. The melts were prepared and held in a No. 8 Tercod crucible holding approximately 4 lb of metal. The manganese was added either in the form of a prealloyed ingot (Dow M) containing about 1.5 pct Mn or by the use of a flux (Dow 250) containing manganese chloride. In calculating the flux additions, it was assumed that the manganese introduced would be equal to 22 pct of the total weight of the flux. Temperatures were measured with an iron-constantan thermocouple enclosed in a seamless steel tube, the lower end of which was welded shut. This protection tube also served as a stirring rod. The samples ladled from the upper portions of the melts at the various intervals were analyzed for aluminum, manganese, and iron. When making the alloys which were to be used for the determination of the solidus, 2½ in. diam tilt mold ingots were cast, scalped to 2.0 in. in diam, and extruded into ? in. diam wire. The principal impurities in the melts for this investigation were iron and silicon; their total not exceeding 0.03 pct. Portions of the wire, approximately 2 in. in length, were enclosed in stainless steel capsules for protection from the atmosphere. Bundles of these capsules, with a dummy capsule containing an iron-constantan thermocouple, were heated inside a large steel block (acting as a heat reservoir) in a closed circulating-air type electric furnace. At ap- propriate times, the capsules were removed and quenched in water. The wires were examined metallographically to determine the temperature of initial melting. Short times at temperature were used at the beginning for wire specimens of all alloys to obtain quickly the approximate temperatures at which melting could be first observed. When approximate solidus temperatures had thus been determined, equilibrium heating was attempted. This equilibrium heating consisted of an 8 or 16 hr period at a temperature, about 50 °F below the lowest temperature at which melting occurred when short heating cycles were used, followed by further heating for 1 hr periods at consecutive 10" higher temperatures. The theory for the method of stress-rupture at incipient melting has been well covereda and its limitations are recognized. Thus, if the interfacial tensions are such that the first minute quantity of liquid is "bunched up" at the grain boundary junctions instead of spreading out along the grain boundaries,³ temperatures higher than the solidus are required before melting will be manifested by rupture of the specimen. This point will be elaborated later. Specimens of the wires with a reduced section (approximately 1/16 in. diam) were suspended vertically in a tubular furnace. The setup used is shown in Fig. 1. The clamp holding the specimen was made from alumel thermocouple wire and the thermocouple was thus completed across the specimen by attaching a chrome1 wire to its lower end. Temperatures were read from a Speedomax recorder used in conjunction with a calibrated thermocouple. The small weight attached to the specimen and a vibrator attached to the furnace tube, to aid in distributing the molten constituent along the grain boundaries, were used to bring about rupture at a temperature closely approximating the solidus. The specimens were heated at a rate of about 5°C per min. The rupture of the specimens was indicated both by sound and by the action of the recorder. An argon atmosphere containing a small amount of SO² was used for protection of the specimen. The assembly was taken out of the furnace immediately following rupture and the specimen removed. Some of the broken specimens were examined metallographically and will be referred to later. Results and Discussion Fig. 2 shows a set of typical time-composition curves for liquid samples of the Mg-Al-Mn alloys used for the settling tests. The data as presented

Jan 1, 1952

By R. Maddin, C. H. Mathewson, W. R. Hibbard

Recent publicationsl.2 establishing the presence of cross-slip in strained metallic single crystals oriented wholly within the area of single slip as predicted from the generalizations of Taylor and Elam3 described these markings as they appeared during the initial stages of the deformation process. At that time, the plane having a common glide direction with the primary slipping plane was reported as the cross-slip plane although the specific direction was not confirmed. Consequently, in continuation of the research, it seemed advisable to investigate the micro-graphic appearance of cross-slip together with the Laue back-reflection X ray analysis and stress-strain data during the later stages of the deformation process. Accordingly, a single crystal of brass (72.75 pct Cu, 0.01 pct Fe, 0.01 pct Pb, 27.23 pct Zn) was polished mechanically and repolished electrolytically after the manner described in the earlier paper.&apos; Three pairs of flat surfaces, parallel to the specimen axis, and (1) perpendicular to the plane containing the pole of the primary glide plane and the specimen axis, (2) perpendicular to the plane containing the pole of the cross-slip plane and the specimen axis, and (3) perpendicular to the plane containing the slip direction and the specimen axis, were polished mechanically and repolished electrolytically, resulting in a final minimum gauge diameter of 0.4864 in. in a gauge length of 3.36 in. The specimen was elongated in tension and load-extension readings were taken following the method described in the initial investigation.&apos; Observed reorientations were obtained from a series of Laue back-reflection photograms at the center and ends of the gauge length and at various positions around the circumference of the specimen. These were interpreted after the manner of A. B. Greninger.4 Cross-slip (Fig 1 and 2) was found with the first appearance of the primary slip clusters and usually joined members of these clusters. In addition, a third set of entirely different markings (Fig 3) could be noted. The displacement of this third set by the primary slip lines was measured as 8300 at. diam (3.04 microns). Since the specimen was carefully observed at high magnifications before any deformation and no markings of any type could be noted, it would appear that this third set was formed during the deformation process prior to the initiation of classical primary slip. Additional extensions produced no unusual change in the appearance of either cross-slip or the third set of markings. The number of lines increased with increasing elongation and appeared, generally, in areas where earlier markings were present. The continuity of the clusters of cross-slip lines in Fig 4, 5 and 6 illustrates that they are neither noticeably displaced by nor do they displace the primary lines at this stage. In Fig 7, cross-slip appears in a long narrow localized band approximately 45 degrees from the stress axis. This somewhat resembles a twin band except for the lack of a sharp boundary. After a shear of 0.257, suffcient additional glide occurred on the cross-slip plane to displace the primary slip lines (Fig 8). Generally, where a large number of cross-slip lines could be observed in an area on one flat surface, few cross-slip lines appeared on the diametrically opposite position on the parallel flat (Fig 9). These, of course, were not matched observations on the same glide ellipses. It was extremely difficult to make such comparisons. The third set of markings (Fig 10) was extensively displaced by glide on the primary slip planes. A plot of the width of primary slip clusters versus their displacement of the third set of lines is shown in Fig 11. The slope and the linearity of the plot suggest that each primary glide plane slips to a constant maximum value of shear before further slip is transferred to another plane. A shear value of 0.28 was determined in this case. Heidenreich5 has presented a similar schematic representation of glide for aluminum. After the specimen had attained an elongation of 51.8 pct, corresponding to a shear of 0.973, cross-slip appeared very prominently in certain areas as shown in Fig 12, yet at diametrically opposite positions very little cross-slip could be noted, Fig 13. Classical conjugate slip was found at this advanced stage in the deformation, Fig 14, which corresponds to the axial location shown at 12 in Fig 15. It should be noted that cross-slip occurs within the conjugate slip clusters and on the same plane as the cross-slip associated with the closely spaced primary lines which constitute a background in less distinct focus. The third set of markings noted at all stages in the deformation of the

Jan 1, 1950

By E. Mcl. Tittmann

Deep-seated human instincts urge us to positively mark the passage of time. We celebrate the passage of each year. Years give way to decades, and decades to half centuries and centuries. At all these mileposts we are inclined to pause, take a look around and catch our breaths before embarking on the next leg. We are at such a point now and this meeting I am sure will give direction to the road ahead into the decade of the seventies. In looking around at this point, 1973, it is obvious to all of us that the environment in which we must mine, mill, smelt and refine lead and zinc has radically changed. These changes have, of course, occurred over a long period of time. They have, however, all been in the same general direction. They have all had the same motivation. The period of greatest contrast is probably the fifteen years just before World War II and the fifteen years following the end of that war. I thought that I might review briefly with you what seems to me to be four of the more important changes that have developed since World War II that profoundly affect our activities in the lead and zinc industry. I mentioned before that all these changes have been in the same direction; that is, they have all tended to restrict our freedom of action in pursuing our objective of producing lead and zinc on a competitive basis at a profit. Consequently, in discus- sing them you may think that I am merely viewing with alarm. This is not the intent. This is merely supposed to be an objective analysis. I think it appropriate before discussing these trends in de- tail to examine the position of lead and zinc today.

Jan 1, 1970

By E. Mcl. Tittmann

Deep-seated human instincts urge us to positively mark the passage of time. We celebrate the passage of each year. Years give way to decades, and decades to half centuries and centuries. At all these mileposts we are inclined to pause, take a look around and catch our breaths before embarking on the next leg. We are at such a point now and this meeting I am sure will give direction to the road ahead into the decade of the seventies. In looking around at this point, 1979, it is obvious to all of us that the environment in which we must mine, mill, smelt and refine lead and zinc has radically changed. These changes have, of course, occurred over a long period of time. They have, however, all been in the same general direction. They have all had the same motivation. The period of greatest contrast is probably the fifteen years just before World War II and the fifteen years following the end of that war. I thought that I might review briefly with you what seems to me to be four of the more important changes that have developed since World War II that profoundly affect our activities in the lead and zinc industry. I mentioned before that all these changes have been in the same direction; that is, they have all tended to restrict our freedom of action in pursuing our objective of producing lead and zinc on a competitive basis at a profit. Consequently, in discussing them you may think that I am merely viewing with alarm. This is not the intent. This is merely supposed to be an objective analysis. I think it appropriate before discussing these trends in detail to examine the position of lead and zinc today.

Jan 1, 1970

By Ralph Arnold

Since 1915, when Elk Basin field was brought in, eight oil fields have been developed in Montana and the production has arisen from 50,000 bbl. in 1916 to 8,000,000 bbl. in 1926. The production for 1927 was 5,121,600 bbl. and the total up to the end of 1927 was 27,138,239 barrels. The eight fields, with their year of discovery are: Elk Basin, Carbon County (1915); Devil&apos;s Basin, Petroleum County (1919); Cat Creek, Petroleum County (1920); Soap Creek, Big Horn County (1921); Kevin-Sunburst, Toole County (1922); Lake Basin, Stillwater County (1924); Pondera, Pondera and Teton counties (1927); and Bannatyne, Pondera and Teton counties (1927). About 170 wildcat wells have been drilled in the state of which 8 were successful and 162 gas wells or dry. Hence, only one out of 21, or 5 per cent. of the wildcats have been successful. The average depth of the wells has been 1600 ft. and the average cost $32,000 apiece. • Up to Jan. 1, 1927, a total of 1376 wells have been drilled in the producing oil and gas fields of the state, of which 904, or 66 per cent., were successful oil wells; 82, or 6 per cent. were gas; and 390, or 28 per cent, were dry. The percentage of dry wells is excessive as compared to the wells in other states, due to the uncertainties of limestone reservoir rocks. The total production of oil to Jan. 1, 1927, has been 22,016,639 bbl. and of gas 7,265,330,000 cu. ft. The average price at the well for the oil has been $1.47 per bbl. and for gas about 4 c. per 1000 cu. ft. The value at the point of consumption has been about 23 c. per 1000 cu. ft. The total revenue derived from crude oil has been $32,277,119, and from gas 8350,613, or a total income to the producer of $32,727,832. Each well drilled in the state has already (to Jan. 1, 1927) averaged a return of over $21,000. The total number of domestic (Montana) oil and gas companies organized, since the first in 1885, has been 844, of which 702 are still alive and 142 dead. Oil and gas companies registered for operation within the state to Jan. 1, 1927, but with outside charters, are 143, of which 66 are alive and 77 are dead. Outside the few distributing companies, which are included in these figures, the grand total of 997 companies which have

Jan 1, 1928

Volume LIV has been shipped to all members whose clues were paid on or before Feb. 10, 1917. The next shipment will be made the latter part of April to all those whose dues were paid on April 1, 1917.

Jan 4, 1917

A Little Book on the Assaying of Gold, Silver, Copper, and Lead. Also on How to Assay and Work profitably All Minds of Metal. Complied with great care for the benefit of all mintmasters, assay masters, gold= smiths, miners, and dealers in metals.

Jan 1, 1949

FREDERICK LAIST, * Anaconda, Mont. (written discussion?).-All who are interested in the treatment of oxidized copper ores by leaching have been awaiting the publication of this paper, which comes up to our expectations in all respects. Messrs. Tobelmann and Potter are to he congratulated upon the excellent way in which they have set forth the workings of the process as applied at Ajo. Numerous attempts have been made to apply the electrolytic copper process but all have failed, except the installation of the Chile Copper Co., at Chuquicamata. Some of these failures were due to insufficient financial backing and inadequate ore reserves, which necessitated opera-

Jan 5, 1919

By J. J. Jakosky

The strategic importance of the metallic minerals in our industrial economy, and the declining rates of discovery have focused attention on means of exploration for new mineral deposits. A consideration of exploration techniques leads to an attempt to evaluate the effectiveness of geo- physics as a tool for mining exploration. One means of evaluation will be to compare the use of geophysics in petroleum exploration with its possible uses in mining.

Jan 1, 1949

Jan 1, 1943

Jan 1, 1893

Jan 1, 1916

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Jan 1, 1943