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By A. B. Kinzel

IT is with sincere appreciation and a deep sense of responsibility that I accept the honor of delivering the Howe Memorial Lecture. In our time metallurgical research has delved into phenomena ever more complex in character, so that much of this work must be done by organized teams. We, of the Union Carbide and Carbon Research Laboratories and the Electro Metallurgical Co., are truly a team and the lecture which is to follow is due largely to a few of the outstanding members of that team here cited and well known to you in their own right: John Lamont, whose work deserves special recognition, Walter Crafts, William Forgeng, William Binder, Robert Fowler, and David Swan. Thus it is a fitting pleasure to accept this honor for the research institution which I represent. Henry Marion Howe was truly inspirational and his breadth of view was such that he could use either the method of rigid proof or implied mechanism to further the broad understanding. But perhaps his outstanding characteristic was his sound judgment and his ability to weigh observations. The following is replete with observations and judgment as to their implication. We would like to feel that it is the type of dissertation which Howe, himself, would have enjoyed. Chromium carbides in stainless steel have, in a sense, been a key to the progress of the stainless steel industry. Brearley's first stainless steel, containing approximately 0.30 pct C, was successful because it differed from previous Fe-Cr alloys in that the carbides were present in such amount and form as to provide the stainless and cutting properties. Again, the 12 pct Cr die steels with a carbon content of 1.5 pct or more achieved their properties by virtue of the form and distribution of the chromium carbides. In the straight chromium steels with from 12 to 25 pct Cr, chromium carbide amount and distribution are once more the determinants with respect to physical properties and corrosion resistance. In each of the cases just cited the role of the carbide is in essence similar to that of iron carbide in carbon steel and this story is so well known that we need not dwell on it. In the austenitic stainless steels, the chromium carbide plays only a minor positive role with respect to mechanical properties, and for corrosion resistance the objective is to achieve maximum homogeneity. Thus the tendency has been to ever lower the carbon and correlatively the chromium carbide content of the austenitic steels. Today stainless steels with carbon less than 0.03 pct are beginning to find their true place, and this is being aided in major degree by our Company's introduction of a new type of ferrochromium having negligible carbon. The role of carbon in these austenitic steels has long been recognized, and a truly enormous amount of research has been devoted to the subject. Much has been learned about corrosion resistance, but the attack on the problem from the point of view of carbide precipitation and the nature thereof has left much to be understood. Because of its fundamental importance to the future of stainless steels, further study of the mechanism of carbide formation in austenitic steels is of interest. In the 18-8 Cr-Ni steels, which are typical of the austenitic class of steel, carbon is soluble in the aus-tenite to the extent of approximately 0.15 pct at 1832°F (1000°C). The solubility becomes less with decreasing temperature, so that at 1652°F (900°C) the solubility limit is approximately 0.06 pct, at 1472°F (800°C) it is about 0.03 pct, and at 932°F (500°C) it is approximately 0.01 pct. Obviously this is the ideal situation for the classical precipitation phenomenon. It is true that, in a sense, 18-8 austenite resulting from annealing is in a metastable state, and the phenomenon of ferritic precipitation from this austenite should be considered. However, in a so-called fully austenitic 18-8 steel this is secondary with respect to the carbides and can be neglected. A wide variety of chromium carbides is known. Only one chromium carbide, Cr,,C,,, frequently referred to as Cr,C, has been found in unmodified low carbon 18-8 steel. This, fortunately, simplifies the study of the precipitation phenomena. For this study an A.I.S.I. type 304 stainless steel of commercial quality was selected. Analysis showed C 0.07 pct, Mn 0.49 pct, Si 0.33 pct, Ni 9.34 pct, Cr 18.91 pct, and N 0.033 pct. As expected with this composition the steel was homogeneous after annealing except for a few pools of ferrite, which were disregarded in that their location was not coincident with subsequent carbide precipitation areas. On corrosion testing the steel was normal and typical of good commercial quality. Specimens 1/2xlx4 in. were annealed and subjected to precipitation heat treatment for 100 hr at 100" temperature intervals from 1000° to 1500°F and for ten selected intervals ranging from 5 min to 64 hr at 1300°F. These blocks were then cut into small pieces for metallographic studies. The first problem

Jan 1, 1953

By E. T. Hayes, A. H. Roberson, M. H. Davies

R. F. Dornagala and D. J. McPherson (Armour Research Foundation, Chicago)—I should like to compliment the authors for a workmanlike job in determining the partial phase diagram of a system comprised of two rnetals which are certainly not easy to work with. We are completing work at Armour Research Foundation on an Atomic Energy Commission-sponsored project for the determination of eight zirconium binary diagrams. Work on the Zr-Cr system has been completed and should be published within the next year. For our work, Westinghouse Grade 3 iodide crystal bar served as the zirconium melting stock. Johnson-Matthey, electrolytic chromium, specially treated for oxygen removal, was employed. The overall constitution of the system determined at Armour Research Foundation is in very good agreement with the present work. We found a eutectic at 18 pct Cr and 1280 °C, somewhat lower than the value reported. This temperature was confirmed by thermal analysis, incipient melting studies, and regular isothermal anneals. The eutectoid was located close to 1 pct Cr and 835°C by metallographic analysis of annealed specimens. Maximum solubility of chromium in /S zirconium was 4.5 pct at the eutectic temperature. Chromium solubility in a zirconium was less than 0.28 pct at all temperatures. We found the compound at 53 pct to melt around 1700°C, with an open maximum, but determined its crystal structure to be hexagonal close-packed (MgZn, type). The lattice parameters were in excellent agreement with those determined by Wallbaum in 1942. The diagrams are in substantial agreement, and .part of the differences are undoubtedly due to the use of different zirconium melting stock. M. K. McQuillan (Birmingham, England)—I read this paper with a great deal of interest, as it covered the same field as some work of my own.' There are a number of points in the present paper on which I would like to comment. First, I should say that I, too, used zirconium prepared by magnesium reduction of the tetrachloride and electrolytically prepared chromium, and melted the alloys in a Kroll-type arc furnace. The purity of my alloys should, therefore, be comparable with the purity of those of the present authors, and any differences in our observations would not be expected to be attributable to this cause. The differences between my observations and theirs concern the presence of the eutectic, the temperature of the eutectoid, and the melting point of the compound. I would be very much interested in any further evidence the authors may have for the occurrence of the eutectic at 1380°C. During the course of my work I noted that a number of my alloys containing 60 to 90 pct Zr melted at about 1400 °C, and for a time assumed that a eutectic occurred at this temperature as described in the paper. On further investigation, however, I found that the structures of the as-melted alloys could not be made to fit in with this interpretation of the system. If a eutectic exists in this region of the system it would be expected that the as-melted alloys would show the usual type of cast structure, i.e., dendrites of the compound plus eutectic. This, however, does not occur, as may be seen from Fig. 9. The compound seen there is not dendritic in form, and the remaining material is by no means certainly eutectic. It may be argued that a compound such as ZrCrl would not form dendrites but would tend to crystallize in geometric shapes. In this case, however, I have evidence to the contrary, as on the chromium side of the compound, where a eutectic occurs at about 1545"C, the compound formed from the liquid takes on a conventional dendritic form, and the eutectic is observed in the interdendritic spaces in the usual way. There is no reason to suppose that the compound would behave differently in an alloy lying on the zirconium side of the compound composition if a eutectic existed there too.

Jan 1, 1953

By Ruddle R. W.

The slags produced in copper smelting are largely composed of silica and ferrous oxide and may therefore be regarded as essentially ferrous silicates. A fair amount of information is available on the constitutions of the liquid slags used in copper smelting and, in this connection, the large volume of work being carried out on steelmaking slags should be helpful. Constitutional diagrams are available for most of the principal systems involved (SiO2-FeO; SiO2-FeO-Al2O 3; SiO2-FeO-CaO; SiO2-FeO- MgO; and SiO2-FeO-CaO-Al2O3) and these show that additions of Al2O3 and CaO reduce the freezing points of SiO2-FeO slags but that additions of MgO increase the freezing point. A certain amount of information is available on the thermodynamics of slags, but much further work on this subject is required. Modern theories of the constitution of liquid slags deny the existence of molecular compounds but consider that liquid slags are mixtures of various ions such as, Fe2+. O2- and SiO4(4-). Little appears to be known of the reactions between matte and minor constituents dissolved in the slag

Jan 1, 1953

By Kenneth Schellinger

THE terms surface tension and surface energy are well known when applied to liquids and are generally described by referring to the excess energy of the air: liquid interface as a result of unsaturated molecular forces surrounding the surface molecules of the liquid due to the presence of the air phase on one side. Such unbalanced forces produce the familiar water droplet of spherical form and are generally summed up as a surface tension measured in dynes per centimeter which can be shown mathematically to be equal numerically to a corresponding surface energy expressed in ergs per square centimeter. A specific surface energy, however, is best thought of as the energy necessary to produce one unit, of new surface on a substance. Hence, in producing a bubble in a flotation cell the impeller must supply surface energy corresponding to the air: liquid interfacial area on the interior of the bubble. Inasmuch as it is relatively easy to extend or contract the surface of a liquid, there are a number of successful methods for liquid surface tension, or energy, measurement based upon surface deformation. This happy state of affairs does not, however, extend to solids, which are considered to possess surface energies for the same reasons as do liquids, i.e. because of unsaturated ionic bonds at the solid: gas interface. As in the case of the flotation cell producing surface on liquids as new bubbles, it takes energy to produce new surface on solids as new particles. As every mill man knows, this surface is produced on mineral solids in a grinding mill by the action of a tumbling mass of iron balls. But here so much energy usually is wasted by the inefficient action of these balls that a large amount of heat is generated, and the surface energy production may be easily confused with the energy necessary to produce this ineffective heat. The tumbling balls and fracturing minerals ultimately take their energy from a rather large electric motor. It has been variously estimated that from 10 to 20 pct'" only of this energy from the motor does not appear as heat and may be presumed to appear as surface energy on the min- erals present. Such a production of new surface on the mineral phases is accompanied, of course, by a size reduction that is inevitable as more and more mineral interior molecules become surface molecules by the fracture exposure. This size reduction of mineral particles, although the most obvious feature and perhaps the sole object of the milling operation, is from this energy viewpoint the outward manifestation of the production of surface energy only. Measurement of the characteristic surface energies of pure minerals and their various mixtures in ores would be a step towards understanding of the energetics of the commercial grinding operation. In addition, the characteristic surface energy of a mineral is probably a physical property specific for that mineral, and therefore, from a scientific standpoint, should be measured. It is interesting to note that, in contrast to the large body of work on the surface tensions of liquid systems and biological systems, the field of solid surface energies has been neglected. Prior to 1920 it is difficult to find more than one or two references to work on solid surface energies in Chemical Abstracts. Since 1920 such references number somewhat less than 100, while those on liquid systems are numbered in the thousands. Much of this apparent neglect of the field of solid surface energies (the term is intended to be somewhat inclusive at this point and refers both to the solid: gas, and the solid:liquid interface) is because of the lack of a reliable method of measurement rather than any lack of scientific curiosity. It was, and still is, difficult to produce new surface on a solid without the simultaneous production of interior changes in the same solid which may consume part of the energy used. The extension in the surface area can be measured, but the interior crystal-

Jan 1, 1953

By John B. Goodman

A LOW-TEMPERATURE carbonization assay test is described, and factual data derived from this test are presented. The test procedure outlined in this report incorporates a mild-steel retort of improved design, an accurately controlled method of heating, and a complete collection and condensation system for the solid, liquid, and gaseous products of carbonization. The test described establishes, under closely controlled conditions, the relationship of temperature to yields of products on carbonization. Noncoking or weakly coking coals and other carbonaceous material are particularly amenable to testing by the assay. Mass balances of 100 percent± 0.3 are obtainable by this test. It is believed that the efficiency of the test and the accuracy of the type data obtained have been materially increased.

Jan 1, 1953

By F. W. Brown

In 1942 the Explosives Division investigated electrostatic hazards associated with the manufacture, storage, and use of explosives. A report was issued in 19454/ presenting the data on the spark sensitivities of explosives. In 1948, the apparatus was redesigned and rebuilt to make the routine testing of explosives safer and more convenient. The rebuilt apparatus is described in this re-issue of the former report. Included are details of construction and a list of parts. PRINCIPLES OF METHOD In normal procedures without special precautions, it is possible for static charges to be accumulated on individuals or on ungrounded equipment or structures.5/ Static charges may be produced in many ways, but they are most commonly produced by rubbing or successive contact and separation of unlike surfaces, at least one of which is usually an insulator.

Jan 1, 1953

By Paul Pietrokowsky

THE formation of intermediate phases in the solid state reaction of titanium with silicon, germanium. and tin (of subgroup 4B in the periodic table) was the subject of a recent paper.' Further investigation of the system Ti-Sn revealed the presence of a new compound on the titanium-rich side of this phase diagram. Metallographic evidence indicated that this new phase was situated very close to 75 atomic pct Ti. The present work is concerned with the crystal structure of the intermediate phase Ti3Sn. Iodide-process titanium metal, furnished by the New Jersey Zinc Co., was used in this investigation. The metallic tin was received in powder form from Charles Hardy Inc., New York; its purity was 99.80 pct. The titanium rod was machined into small cups 1 cm in diam and about 1.5 cm in height. The tin powder was compacted, melted, and then placed in the titanium cups and alloyed by electric arc melting in a helium atmosphere. The alloys, weighing approximately 8 g, were sealed in evacuated quartz tubes and homogenized at 1030°C for 5 days. This isothermal heat treatment was terminated by a water quench from the soaking temperature. Filings of the alloyed pellets were sealed in evacuated quartz bulbs and quenched from 1030°C into liquid argon. A 14.32 cm Debye Scherrer X-ray camera was used for the powder diffraction study. The copper radiation was filtered. X-ray diffraction data for the compound Ti3Sn are given in Table I. The data were indexed on the basis of a hexagonal lattice. Good agreement between observed and calculated values of the square of the reciprocal interplanar spacings was obtained with the following expression: (1/d)2 = 0.03810 (h2 + hk + k2) + 0.04410 (l2) Unit cell parameters were calculated by the method of least squares from the reflections (20.3), (22.2), (40.1), and (42.1); ao = 5.916 & 0.004A, co = 4.764 ± 0.004A, and co/ao = 0.805. The relatively small size of the unit cell allowed the unambiguous indexing of most of the reflections from planes of large spacing. An inspection of the assigned indices (Table I) reveals the absence of (hk.l) reflections when 1 2n. A systematic absence of this type leads to the space group C 6/mmc or one of its subgroups. Assuming, for a first approximation, a linear increase in the density of titanium with the addition of tin, it follows that there are two stoichiometric molecules of Ti3Sn per unit cell. The density calculated from X-ray measurements is 5.194 g cm-'. At this point it became clear that Ti3Sn might be isomorphous with Mg3Cd. The 6 Ti and 2 Sn atoms were placed in the following positions of space group D4 6h, C 6/mmc: 6Tiin (h): X 2X 1/4; 22;; 1/4;Xx 1/4;x2x3/4; 2x x 3/4; x x 4; with x = 516 2 Sn in (c): 1/3 2/3 1/4; 2/3 1/3 3/4.

Jan 1, 1953

By O. D. Sherby, J. E. Dorn

SEVERAL years ago Zener and Hollomon1 suggested that the flow stress of metals might be related to the temperature and strain rate in accord with the functional equation: s=s(eeh/rt) [1] at the same state. The Zener-Hollomon relation also contains the significant tacit implication that the energy for activation, AH, is substantially independent of the state of the material. The utility of this method for correlating creep data with tensile data was illustrated in a preliminary reportL on the effect of alloying additions on the secondary creep rates of binary a solid solutions in aluminum as shown for Al-Mg alloys in Fig. 1. Not only do the secondary creep and ultimate tensile properties for each alloy correlate well on this plot but in addition the activation energy, AH = 17,900 R cal per mol. is identical for the various compositions. Similar types of curves correlating the secondary creep rates at 422°K (300°F) with ultimate tensile data were also obtained for a series of dilute a solid solutions of copper, germanium, zinc, and silver in aluminum. In all cases the activation energy for creep, AH, was found to be equal to about 17,900 R cal per mol independent of the type of alloying element or its concentration. The coincidence of the activation energies for these alloys is probably due to the fact that the activation energies for creep are rather insensitive to small composition changes. Alloying additions, as shown in Fig. 1, however, increased the stress necessary to obtain equivalent values of ee?H/RT. Thus the stress level in curves of the type represented by Fig. 1 gives the relative creep strengths of the various alloys. Inasmuch as these correlations between creep and tensile data were obtained for creep tests at 422°K, it appeared advisable to ascertain the range of secondary creep rates and temperatures over which correlations between creep and tensile data could be made on the basis of the Zener-Hollomon relationship. If, for example, the activation energy changes with different ranges of creep temperatures, the utility of the proposed analysis would be severely weakened. But if AH is constant not only for all dilute alloys, but also over wide ranges of temperature and secondary creep rates, confidence will be developed not only in the broad utility of the Zener- Table I. Chemical Analysis':' and Grain Size of Alloys Mean Grain Residual Impurities. Wt Pct Diam- Alloying Atomic-eter, Element Pct Si Fe Cu Mg Mn mm Aluminum 99.987 0.003 0.003 0.006 0.001 0.25 Magnesium 1.617 0.003 0.004 0.006 0.26 Copper 0.101 0.003 0.003 0.0006 0.001 0.29 Zinc 1.616 0.003 0.005 0.007 0.001 '0.26 * The authors express their appreciation to the Aluminum Company of America for the preparation and chemical analyses of these alloys. Hollomon relationship, but also in its theoretical justification. The following investigation was instituted in order to ascertain the range of validity of the Zener-Hollomon relationship when it is applied to creep and tension data. Materials, Equipment, Technique In view of rather extensive correlatable data now available on the plastic properties of a series of binary a solid solutions of magnesium, copper, germanium, zinc, and silver in aluminum, these alloys were again selected for the present investigation. Previous reports have already covered the tensile properties of these alloys at subatmospheric temperatures," and at elevated temperature," as well as their fatigue properties at atmospheric temperatures, nd their creep properties at 422°K.' Resistivity measurementsa as well as precision lattice constant determinations? evealed that these alloys are a solid solutions. After homogenization. 0.100 in. thick sheets were rolled to 0.070 in. in thickness and recrystallized to about the same grain size. Since the details of these treatments were reported previously," they will not be repeated here. In order to appropriately reduce the scope of creep tests in this investigation only the typical alloys shown in Table I were investigated. All creep specimens were machined such that their tensile axes were in the rolling direction of the 0.070 in. sheet stock. The gage section was 2 in. long and 0.500 in. wide with a reduced section of 3.50 in. Creep strains were measured by means of rack and pinion type extensometers with a sensitivity of 0.005 in. per division. Readings were estimated to 1/10 of

Jan 1, 1953

By J. L. Carne

ORE control is a matter of planning and supervision based on a foreknowledge of the content and distribution of ore. The Inspiration orebody is predominately a copper-sulphide blanket, overlain by an oxidized zone of copper silicates, copper carbonates, and barren capping. Most of the ore is treated by leaching, and the optimum requirement of this method is the goal toward which the mining schedule is aimed. Both open-pit operations and underground mining are used. The problems of ore control at Inspiration are: I—maintenance of metallurgical balance, 2—conservation of oxide ore, and 3—mining out of the orebody at an average grade which parallels that of the reserve figure. Prior to the fall of 1926 all of the Inspiration division ores were treated by flotation, but the mixed ores of the Live Oak—Keystone section carried too large a proportion of copper in the form of chrysocolla for satisfactory flotation. For this type of mixed ore the leaching process now in use had been worked out, and the plant was put into operation in the fall of 1926. The process is known as the ferric sulphate leach, and the leaching solvents contain both ferric sulphate and free sulphuric acid. Sulphide copper in the form of chalcocite is leached by the ferric sulphate, and the oxidized copper minerals are dissolved by the sulphuric acid. From the beginning of operations to the present time the plant has treated some 67 thousand tons of ore having an average copper content of 1.142 pct, of which 0.605 pct has been in the form of oxidized copper minerals. The plant is currently being operated at the rate of 11,500 tons per day, 7 days per week. However, this tonnage is produced in 6 days of mine operation. The average current grade is approximately 1 pct copper, of which about 50 pct is present as oxidized or acid-soluble copper. Close control of metallurgical procedures is a vital factor in operation of the plant and is in turn dependent upon careful regulation of feed. An excess of sulphide copper requires the presence of more ferric sulphate in the leaching solvents. On the other hand, an excess of ferric sulphate in the presence of a low sulphide feed seriously reduces the efficiency of electrolytic precipitation in tank house operations. This condition must be avoided at all costs. An additional factor must be considered. It is known that the sulphide content is predominant in the ore which remains in the reserve. To maintain the necessary sulphide-oxide proportion, so that the entire reserve will mine out at both a grade and a sulphide-oxide ratio that will be permissible throughout the remaining life of the property, it is obvious that the oxide reserve must be currently preserved to as great an extent as possible. Fortunately much of the oxide reserve is found in the open-pit operation. This happy circumstance adds flexibility to the procedure and makes it possible to maintain the close regulation necessary to insure best overall results, both mining and metallurgical. The two ore streams from the pit and underground operations join at the coarse-crushing plant, and proper control must be exercised before the ore reaches this point. The open pit is currently providing about 55 pct of the ore and underground operations the balance of production. Both operations are under a single superintendent so that the closely interrelated problems may be more readily controlled. The least flexible of the two producing units is the underground mine, where the mining method is block caving. Although a block of ground may be undercut and developed, characteristics of the material determine its caving action. The ore in the chutes must be drawn. The area currently mined from underground is in a zone predominately sulphide and is generally

Jan 1, 1953

By O. J. C. Runnalls, L. M. Pidgeon

Some observations on the kinetics of the iodide process are reported. The deposition rate is geometry-sensitive in a system containing a finely divided titanium charge. Further, results indicate that the iodine diffusion rate influences the velocity of the process. The nonvolatile iodide, Til,, forms in the hot filament zone, thus removing iodine from the cycle. TITANIUM metal of 99.9 pct purity may be prepared using a refining technique originated by Van Arkel and de Boer.' The purity of this metal, commonly called iodide titanium, exceeds that produced by any known process. In a recent application, the method was employed by Gonser et al.² to prepare titanium rods up to 2 to 3 cm in diam. In the Van Arkel-de Boer system, the relative influence of the fundamental mechanisms: l—production of titanium iodides, 2—gaseous countercurrent diffusion, and 3—decomposition, on the deposition rate have not been clearly established. Blocher and Campbell" have indicated that the controlling step in the process under practical conditions of operation may be the reaction rate of iodine with the crude metal. Fast' reported that crude titanium metal reacted with iodine rapidly, even at room temperature, in his apparatus. Little has been reported on the effect of gaseous diffusion or decomposition on the deposition rate. It is these aspects of the process about which this investigation is centered. An attempt has been made to separate these latter effects from those due to the formation of the iodides at the crude metal surface by a division of the experimental program. Reaction of Iodine with Titanium Apparatus: In the investigation of gas-metal reactions of this type, the chemical reactivity of the halogen and halide vapors dictates the use of all-glass apparatus. In such a system standard techniques for measuring reaction rates are difficult to employ. Here, a simple apparatus was devised (Fig. 1) so that some indication of the reactivity of titanium powder with iodine vapor could be obtained. A stream of iodine gas was evolved from a bulb of controlled temperature and passed over a sample of titanium powder heated in a horizontal tube furnace. The product of the reaction, TiI4, volatilized and was condensed outside the furnace in a series of four glass bulbs, each cooled to room temperature in turn. Preliminary experiments indicated that distillation was retarded in a sealed evacuated system due to a pressure build-up in the condensing end of the apparatus. Hence, the system was pumped continuously using a mechanical pump and two oil diffusion pumps in series, through a liquid air trap. The iodine bulb was made large and a capillary restriction was inserted between the titanium bulb and the condensers so that the iodine pressure over the metal would approach the equilibrium pressure over solid iodine crystals. The effect of this restriction on the evaporation rate of TiI4, was determined separately. The iodine bulb was heated in an oil bath controlled to ±2°C. The titanium bulb temperature was automatically controlled to ±5°C. Procedure: About 200 mg of —30 mesh titanium powder, weighed to 0.1 mg, was placed in the reaction bulb after part B had been joined to part A. The powder was tapped into a long (5 cm) shallow mass along the bottom of the tube. Two chromel-alumel thermocouples were inserted into the magnesium radiator which was clamped to the reaction

Jan 1, 1953

By Gearge C. Wallick

This paper describes experimental procedures for the calibration of capillary tubes to be employed as comparison standards in gas flow-rate measurements and considers several types of flow which were observed in the calibration of seven capillaries of varying diameter. It is shown that under certain experimental conditions deviations from Poiseuille flow are observed which may not be attributed to turbulence, and that this flow behavior may be described empirically by introducing the classical kinetic energy correction into the Poiseuille equation. INTRODUCTION Techniques have been developed for the measurement of the volume rate of flow of nitrogen through glass capillary tubes as a function both of the differential pressure applied and of the absolute gas pressure. Capillary tubes thus calibrated are frequently used to determine the rate of gas flow through a porous sample in the measurement of slip-corrected permeability. The purpose of this note is to describe the calibration procedure and to discuss some observed deviations from the ideal flow behavior predicted by the Poiseuille equation. EXPERIMENTAL PROCEDURE The volume flow rate of nitrogen as a function of the differential pressure was determined experimentally for a series of seven glass capillary tubes of varying diameter. As is shown in Table 1, the capillary radii in the series ranged from 0.004 cm for K1 to 0.07 cm for K7. The capillary tubes were cut from capillary tubing purchased on special order from several manufacturers and the bore radii were determined by microscopic measurement. The gas volume flow rate was measured for each capillary tube at a series of differential pressures in the range from 0 to 3 cm of mercury and at average absolute pressures of 1.0, 2.5, 4.0, and 6.0 atm. Experimental Procedure for Small Capillaries A schematic diagram of the apparatus used to calibrate the three smallest capillaries, Kl, K2, and K3, is shown in Fig. 1. By means of a standard Ruska Instrument Corp. volumetric pump (equipped with a synchronous motor drive, two stages of gear reduction, and a quick-change lathe gear box), nitrogen was displaced by mercury from a metal cell immersed in a constant-temperature bath. The pump, the line to the cell, and a part of the cell were filled with mercury. As mercury was forced into the cell, it displaced nitrogen which passed through the capillary tube being calibrated and into a large container with a volume of approximately 30 liters. Since the volume of this container was very large compared to the total volume change of the gas resulting from the action of the displacement pump, the absolute pressure of the system was essentially constant throughout any one run. Prior to any determination this pressure could be set at any desired level by means of an auxiliary nitrogen cylinder. The differential pressure across the capillary was measured with a Meriam Red Oil manometer and recorded together with the corresponding pump displacement rate which was equal to the gas flow rate. By repeating this process for a series of different displacement rates at each of the absolute pressures of interest, the data necessary for plotting the calibration curves for capillaries K1, K2, and K3 were obtained. All calibration measurements were made in a constant temperature room to minimize errors due to temperature fluctuations. In each run. the flow was maintained until equilibrium was established. Experimental Procedures for Large Capillaries The flow rates through Capillaries K4, K5, K6, and K7 required to obtain the pressure drops desired were larger than could be obtained from available constant displacement pumps, and it was thus necessary to employ an alternative calibration procedure. The arrangement of apparatus used in calibrating these capillaries at an average pressure of one atmosphere is shown in Fig. 2. Each capillary was calibrated by flowing nitrogen through the capillary and recording the differential pressure as a function of the flow rate. 'The differential pressure was measured with a Meriam Red Oil manometer and the flow rate was determined by collecting the effluent gas over water at constant pressure and recording the increase in volume per unit time after an equilibrium had been established. Appropriate corrections were made for the

Jan 1, 1953

By R. A. Morse, C. R. Stewart, F. F. Craig

This paper preFents the results of a series of model flow test on a number of large limestone cores, having different pore configurations. For limestone cores having substantially sandstone type porosity, the production characteristics for solution and external gas drives are similar. For cores whose pore spaces were microscopically heterogeneous (i.e., consisted of combinations of solution cavities, matrix. and fissures), the production characteristics lor solution and external gas drives vary widely. The degree of divergence between gas-oil relative permeability relationships calculated from solution or external gas drive tests is an indication of heterogeneity of rock pore structure. The results of water floods on cores depleted by solution gas drive for each of these two general types of limestone porosity are also shown. Generalizations are made on the water flood recovery that could be expected from each of these two types of limestone porosity. The similarity between solution drive field performance and model solution drive performance on cores from the same formation is shown for several cases. This indicate? the feasibility of predetermining limestone field performance from such large core tests. Photomicrographs of plastic-impregnated rock thin sections of the samples tested are presented as an aid in understanding the flow test performances. INTRODUCTION During the past 15 years. reservoir engineers and research workers have developed methods of testing rock and fluid samples and applying the results, through calculation, to allow reasonably satisfactory predictions of oil recoveries and performances to be expected in sandstone oil recervoirs. It has been determined that representative fluid flow data can be obtained on rock samples as small as three-fourths in. in diameter by one in. long in most sandstones. However, little has been accomplished toward the laboratory determination of fluid flow characteristics in limestones. There has been a great deal of speculation as to the influence of variations in pore size, shape, and degree of interconnection upon oil recovery processes, and a great deal of thought has been given to the interpretation of limestone field perfomance. It has been generally recognized that predictions of reservoir performance based on oil displacement tests on small limestone core samples the size of those used for sandstone tests can often be misleading because of the improbability of obtaining a representative sample in such a small core. Obviously, if there are present in the rock, pore openings of the magnitude of 1/16 in., or fractures or solution channels up to one in. or more in length, it will be impossible to cut any sample less than one in. in any dimension which would represent the flow geometry of the gross rock system. In some formations, the individual openings in the rock are of such size that it would be impossible to obtain a good sample of the flow system even in the total core available from conventional-sized well cores. However, by increasing to the maximum the size of the sample used, it should be possible to obtain representative flow data from the majority of limestone reservoir materials which can be used for prediction of future primary production performance or response to be expected from secondary recovery measures. The only alternatives to obtaining good laboratory test data to serve these purposes are extrapolation of primary performance data obtained by partial depletion of a field, or obtaining information from pilot tests. It has been shown previously, and will be demonstrated further by the work reported in this paper, that extrapolation of solution gas drive performance for an estimate of gas injection response can be very misleading in reservoirs of heterogeneous type porosity. Although it cannot be expected that laboratory information can ever eliminate the necessity of small-scale pilot operations, it is expected, as is now the situation with sandstone reservoirs, that laboratory tests should provide reliable information for screening of

Jan 1, 1953

By J. D. Little

"THE SALMO PROPERTIES of Canadian Exploration, Limited comprise forty-one Crown-granted mineral claims situated on Iron mountain between Sheep creek (on the north) and Lost creek, some eight miles southward from Salmo, in the Nelson mining division (see Figure 1). On these claims there are at present four operating mines. These are, from north to south, the Dodger, Feeney, and Emerald, all tungsten mines, and the Jersey, a lead-zinc mine, about 7,000 feet south of the Dodger. About midway between the Dodger and the Jersey is a fifth mine, the Emerald lead-zinc mine, which was the first producer in the area but has been inactive since 1926. The locations of the mines are shown in Figure 2.Records of prospecting and claim staking on Iron mountain -which owes its name to the presence of large iron-stained outcrops -go back to 1895. The first recorded owner of the claims that form the old Emerald lead-zinc mine was John Waldbeser who, in 1908, did considerable work and produced 426 tons of lead ore valued, at the then price of lead, at $7,000. This ore was chiefly lead carbonate and was taken from the surface outcrops of two bands of ore that form the Emerald orebodies. In 1909, the Emerald was the largest lead producer in the Nelson mining district."

Jan 1, 1953

By C. R. Sandberg, C. A. Connally, N. Stein

This paper describes the results of volumetric efficiency tests on oil well pumps handling gas oil mixtures. The work was performed in a large scale, above ground unit wherein test conditions could be accurately controlled and measured. The main variables studied were gas/oil ratio (including gas from solution and free gas mixed with oil), pump compression ratio, pump stroke length, pump speed, and clearance volume between the valves at their closest approach. Results are presented for two different pumps and for oils of two viscosities. Relatively small amounts of gas entering the pump resulted in large decreases in volumetric efficiency. Under conditions where the pump was operating at reduced efficiency because of the presence of gas, it was found that variation in the clearance volume between the standing and traveling valves had a considerable effect on pump efficiency level. This effect of the valve clearance volume was found to be significantly altered by the viscosity of the oil used in the tests. The effects on pump efficiency of the other variables studied were found to be relatively small over the range of conditions utilized. INTRODUCTION The production of oil by pumping is often hampered by low volumetric efficiency. A direct increase in lifting costs results from low volumetric efficiency. An indirect increase in lifting costs, probably greater than the direct increase, results from additional wear and tear on pumping equipment and from the down-time necessary for the repairs which can be traced to low-efficiency operation. Both increases in lifting costs tend to reduce economically recoverable oil. A number of different factors can contribute to low pump efficiency. A known basic cause of low efficiency is the presence of free gas in the pumped fluid. Pump volumetric efficiency is calculated only on the basis of liquid pumped and because any free gas pumped is discounted, this volume of free gas would represent a loss of pump efficiency. However, gas also causes a reduction in pump efficiency because it is a highly compressible fluid. It is known that pumps some- times "gas lock" because of excessive gas-to-liquid ratios in the pump barrel. Little is known of the role of gas compressibility in the intermediate case where the pump is operating at low efficiency. The opinion exists, however, that oil-well pumps tend to operate at higher efficiency with long stroke lengths at low speeds, but no quantitative studies of these pumping variables have been reported. It was believed that a much better understanding of the variables which control pump volumetric efficiency could be obtained and that possibly some suggestions as to the methods for increasing efficiency might be found from a study of the operation of pumps handling gas under closely controlled conditions. Previous investigators have studied the effects on pump efficiency of such factors as oil viscosity, oil temperature, slippage of oil. past pump plungers, pump submergence, valve size and spacing, pressure above pump plunger and fluid vapor pressure. However, none of these published investigations were conducted with pumps being subjected to large amounts of gas such as might be the case in a pumping well, nor did any of the investigations study the effect of variation in stroke length or pump speed. A large-scale teat unit was therefore constructed for studying the operation of pumps handling gas and for evaluating effects of such variables as pump stroke length and pump speed. PROCEDURE AND EQUIPMENT A schematic diagram of the pump testing equipment is given in Fig. 1. A 45-ft length of 6-in. casing is mounted vertically in a 65-ft tower. Sight ports are mounted in the casing at intervals near the location of the pump intake and the liquid level in the casing. These sight ports are fitted with Lucite windows sealed by neoprene "0" rings. The Lucite windows are machined to conform to the I.D. of the casing so that no obstruction to flow is present along the casing wall. The casing is fitted with a tubing head and 2-in. tubing is hung inside the casing. Pumps are seated in a shoe attached to the 2-in. tubing. A 1-in. polish rod is attacked directly to the pump without any intervening sucker rods. The top of the polish rod is attached to the weight carrier, which contains a number of weights to be used to force the polish rod in against tubing pressure on the down-stroke. This is necessary because a long string of sucker

Jan 1, 1953

By Norman A. Grant

"Location and Transportation FacilitiesTHE BEAVERLODGE area of North Saskatchewan is on the north side of lake Athabasca, 500 air miles northeast of Edmonton.The main Eldorado operation and townsite are on the north •side of Beaverlodge lake, which is immediately north of lake Athabasca and is separated from it by only a mile long portage at Lodge bay. The once famous town of Goldfields. Saskatchewan, and the Box property of the Consolidated Mining and Smelting Company of Canada, Limited, are located on lake Athabasca nine mines from Beaverlodge townsite.Previously, all Eldorado freight was delivered by barge at the Lodge Bay portage, hauled across the portage, and across Beaverlodge lake by small Northern Transportation Company barges, which involved many handlings.In 1952 the port of 'Bushell' was established at Black bay. This is a particularly snug harbour, well protected from the main body of the lake and with good foundations for docking facilities. A Butler building, 300 ft. by 60 ft., and tank farms provide storage at the port. A •road from Bushell to the main Beaverlodge operation, a distance of twelve miles through rugged terrain, was built by the Saskatchewan Government. The cost was shared by the Saskatchewan Government, the Federal Government, and Eldorado and other mining companies.Along this road are located the properties of several enterprising mining companies and near the midpoint lies the ambitious budding town of Uranium. This road has made portaging unnecessary and palletized freight loaded at Waterways, Alta., is now loaded directly on trucks at Bushell and delivered to the point of consumption."

Jan 1, 1953

By Jesse O. Betterton

IN the last analysis, two basic factors influence the use of metals and alloys; namely, cost and adaptability to the use under consideration. These are so interrelated that to study the properties of metals or alloys without considering the prices and price trends is quite illogical. Lead has been a cheap metal, selling in 1932 for the extremely low price of 2.56 cents per pound. The cheapness of lead in the past was not due to a particularly abundant supply of the element in the earth's crust but rather to the ease with which it was won from its ores and to the chemical stability of the metal, preventing its dissipation. Today, however, our modern economy has caught up with the distribution of lead in the earth's crust and the price is largely dictated by the supply of concentrates readily available for smelting, and which can be placed quickly upon the market. The demand for lead, particularly in times of stress, has brought the price up to the level of 19 cents in the United States, where the price is controlled by Government decree, and the price has been even higher in the world markets. The higher price for lead has changed the uses for this metal to a marked degree, driving it out of the fields where it is not essential. Lead articles of great antiquity have been found in Egyptian ruins, proving the stability of the element and indicating the basic simplicity of its metallurgy. It is probable that lead was the first

Jan 1, 1953

By W. C. Schroeder

During the post-war period, and particularly during the past few years, coal production has been maintained at a reasonably constant level. This is in contrast to the greatly expanded demand for oil and natural gas. Certain markets for coal, such as the railroad and for home heating, have tended to decrease, but this decline has been offset by an increase in demand for other uses, particularly for electric power. Since the United States has very large reserves of coal and relatively limited reserves of natural gas and oil, from the conservation viewpoint, it would be better if the increased demand were to fall more heavily on coal. Where coal has lost certain markets, the decision has not always been made on the basis of price, and, in fact, in many instances, the markets have been lost where coal could show a price advantage. There are various reasons for this situation but it can be attributed in the main to the preference of certain consumers for the convenience offered by liquid and gaseous fuels. In the production of chemicals such as benzene, phenol, or ammonia, coal still plays an important role. As co-products from coke-oven operations, a wide variety of aromatic chemicals are available. In recent years, however, the production has not been sufficient to supply the demand, and it is not profitable to build coke ovens to make chemicals unless there is a market for the coke as well. As a result, the petroleum industry is beginning to take a stronger part in the production of aromatic chemicals. Natural gas has almost displaced the coke-oven water-gas machine for the production of hydrogen for the synthesis of ammonia, as well as for the synthesis of methyl alcohol and other oxygenated compounds. This information is not new and is given here only as a basis for the discussion of the broad significance of the development of the gasification process. It is clear that if coal is to regain some of its old fuel markets, as well as to maintain a position in the field of chemical synthesis, processes must be available for converting coal to the type of fuel the customer wants, and for a cheap method of furnishing gaseous raw material to the chemical industry. The operation of coke ovens and water-gas machines is not the answer to this problem for at least two important reasons: (1) the limited supply and relatively high price of good coking coals, and (2) the relatively high costs of the combined operations of coking and manufacture of water gas.

Jan 1, 1953

By R. C. Buehl, M. B. Royer

A three ton per day blast furnace using blast temperatures up to 2200°F was operated to recover manganese from open-hearth slag and manganiferous iron ore. The spiegel product containing 12 to 24 pct Mn was blown in a basic converter to high manganese oxide slag as described in the paper which follows this one. HE steel industry, which uses over 900,000 short tons of contained manganese yearly, depends on the maintenance of supplies of manganese from foreign sources such as India, Gold Coast, and Union of South Africa. Domestic ores furnish less than 10 pct of the yearly requirements of metallurgical ores and, unfortunately, the United States has no large, or even moderate, grade deposits that could supply a major portion of the requirements for many years. It may be necessary to obtain manganese from low grade materials, even though the cost is appreciably higher than when imported ores are used. An American Iron and Steel Institute questionnaire prepared in 1949 revealed the startling fact that open-hearth slags contained about as much manganese as is imported annually. The quantity of slag produced each year by integrated steel plants (not including cold-melt shops) and the manganese contained in the slag follows: Flush slag, 4,500,000 net tons a year containing 408,000 net tons Mn; tap slag, 7,230,000 net tons a year containing 364,000 net tons Mn; for a total of 772,000 net tons Mn. Some of this slag is returned to blast furnaces but about 75 pct would be available for the recovery of manganese. In several decades, when many of the present sources of high manganese ores have been depleted, open-hearth slag and manganiferous iron ore may become the major source of the manganese required for steel production. In 1948, manganese-ore imports from the U.S.S.R. were 427,000 net tons or 34 pct of the foreign ore. Imports from this source were only 81,000 tons in 1949. It became evident that adequate stockpiles of manganese could not be accumulated for many years. The Bureau of Mines initiated an extensive research program on methods for increasing domestic production of manganese and entered into a cooperative agreement with the American Iron and Steel Institute for recovering manganese from open-hearth slags whereby the Institute provided additional research funds and trained operating personnel. Description of Process and Equipment Numerous pyrometallurgical and hydrometallur-gical processes and combinations of the two can be applied to the recovery of manganese from open-hearth slag and manganiferous iron ore. The process being developed at the Pittsburgh Station of the Bureau of Mines consists of: 1—Reduction of open-hearth slag in a blast furnace to recover the iron and manganese as spiegel-eisen with 12 to 24 pct Mn. 2—Selective oxidation of the manganese from the blast-furnace metal in a basic-lined converter to produce a high manganese slag with up to 60 pct Mn content, which is a synthetic ore for the production of ferromanganese. This process has the advantage over other processes in that the equipment which would be used, such as blast furnaces and converters, has been highly

Jan 1, 1953

By J. Jones-Parra, J. C. Calhoun

INTRODUCTION The purpose of this paper is to present the results obtained by solving the fractional flow' and frontal advance' equations to obtain oil recovery at water breakthrough as a function of the length of the system being flooded, the linear velocity of injection and the displacing phase viscosity. The method of solution makes use of the stabilized zone concept first presented by Terwilliger, et al3 when calculating saturation distributions in a gravity drainage system. In order to check the calculated results, the equations and method of solution were applied to the system on which Rapoport and Leas' reported experimental data. METHOD OF SOLUTION The solution of the fractional flow equation and the frontal advance equation is obtained by assuming that a water front forms to sweep the oil out ahead of it. There is ample evidence that under the proper conditions a water 'front does form. If this water front is not to dissipate, the water saturations which comprise it must have equal linear velocities. These water saturations are said to comprise the stabilized zone. Equation (2) indicates that for all these saturations and hence fw must plot as a straight line against saturation for those water saturations comprising the stabilized zone. The water saturations lying between the highest in the stabilized zone and the highest that can be achieved in the porous medium comprise the variable zone. Regardless of the numerical value of the length of the system, the variable zone must eventually span all of it, so that for long enough systems in Equation (1) will be small enough to be neglected. Hence, for the saturations in the variable zone Equation (1) can be simplified to In order to determine the composite fw function applicable to the entire range of saturations in the porous medium, it is necessary to find the water saturation which separates the stabilized zone from the variable zone. This dividing saturation must be on the curve defined by Equation (4), and a tangent curve at that point must pass through the initial water saturation to satisfy Equation (3). Hence, the valid fw curve is given by a straight line starting at the initial water saturation, tangent to the curve of Equation (4): and along the curve of Equation (4) from the point of tangency on. The point of tangency determines the water saturation dividing the zones. The length and shape of the stabilized zone can be found by solving Equation (1) for Integrating this expression numerically between any two saturations in the stabilized zone gives the distance separating these two saturations. By repeated integration, the saturation distribution of the stabilized zone can be determined. The total length of the stabilized zone is given by The integral appearing in Equation (5) is a function of the viscosity ratio, the capillary properties of the rockfluid system, the relative permeabilities, and the initial water saturation. Considering these variables fixed and designating the value of the integral by writing caw for and v/60 for q/A; Equation (5) becomes The saturation distribution of the stabilized zone can be integrated over its length and divided by the length to obtain the average water saturation The volume of water in the stabilized zone is then given by The average water saturation in the variable zone can be found by extending the straight line segment of (the segment joining Sw and Sw) until it intersects fw = 1.00. The saturation at the intersection is. This method of finding is nothing more than the graphical solution of the equation The volume of water in the variable zone at breakthrough is then given by Assuming no initial water saturation, the recovery at breakthrough expressed as percent pore volume is given by

Jan 1, 1953

By Pol Duwez, Paul Pietrokowsky

Titanium and vanadium form a complete series of solid solutions at temperatures above 885°C. Below 885°C, vanadium is slightly soluble in a titanium (about 1.5 pct V at 650°C) and a two-phase a plus ß region extends to 18.5 pct V at 650°C. The alloys up to 15.0 pct V transform into a supersaturated a solid solution upon rapid cooling from the ß phase. Above 15 pct V the ß phase may be retained. The temperature at which the ß to a' martensite-type transformation takes place decreases steadily from 850°C for 0.5 pct V to 325°C for 12.7 pct V. IN the transition series of the periodic table, the six elements that have a body-centered cubic structure at all temperatures, namely chromium, vanadium, molybdenum, columbium, tungsten, and tantalum, fulfill the conditions required for the existence of complete series of solid solutions with the high temperature (ß) form of titanium. Up to the present time, complete solubility at temperatures above the a to ß transformation of titanium has been observed in the systems Ti-MO,1,2 Ti-Cb,2 Ti-W,³ and Ti-Ta.³ The two remaining elements, vanadium and chromium, have atomic diameters which are not as near that of titanium as the atomic diameters of the four other elements. Both are smaller than titanium and the difference, expressed in percentage of the titanium atomic diameter, is 12.3 pct for chromium and 8.2 pct for vanadium. On this basis, the least favorable conditions for solid-solution formation are therefore encountered in the Ti-Cr system. The early work on the Ti-Cr system4 revealed that up to about 1100°C the solubility of chromium in ß titanium is limited, and an intermetallic phase exists near the stoichiometric composition TiCr2. It was found later' that a continuous series of solid solutions extends across the diagram at higher temperatures, and TiCr2 forms by solid state reaction. It became apparent therefore that complete solubility would also be present in the Ti-V system. The present investigation confirms this possibility. The iodide-refined titanium used in this investigation was purchased from the New Jersey Zinc Co., New York. According to the manufacturer, a typical analysis of this product is 0.0065 pct Mn, 0.0022 pct Fe, 0.0015 pct Cu, and 0.0042 pct Pb. The Vickers hardness number (10 kg load) of the crystalline bar varies between 55 and 80. The vanadium metal was purchased from the Westinghouse Electric Corp., Lamp Div., Bloomfield, N. J. The purity of this metal is probably above 99 pct V. The oxygen content must have been quite low, since a bar about 1/4 in. square could be cold rolled into a ribbon 0.020 in. thick. To prepare the various alloys on the titanium-rich side of the diagram, the titanium rod was machined into cups 1 cm in diam and about 1.5 cm high. Pieces of vanadium, of the proper weight, were cut from the square bars and placed within the cups prior to melting. On the vanadium-rich end of the diagram, single pieces of the metals, in the proper weight pro-

Jan 1, 1953