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By Stephen Royce

[Stephen Royce.. I .......................... E. S. Moore.. 9 .......................... E. L. Bruce.. 10 ......................... J. E. Hawley.. 11 ........................ L. M. Scofield.. I 2] STEPHEN ROYCE, * Crystal Falls, Mich.Having examined and reported upon the Steep Rock Lake property and vicinity on several occasions for clients, and having kept in touch with the operation from 1938 on, the writer offers the following discussion of the valuable paper by Messrs. Roberts and Bartley, which was so kindly prepared in response to the writer's earnest request, made as a member of the Committee on Mining Geology. ORIGIN OF THE ORES The writer wishes to express complete agreement with the authors that the origin of these deposits was replacement action by hot ascending sulphide solutions of igneous origin, gaining access via the limestone and dolomite breccia channels, and acting mainly to replace the dolomite and limestone breccia with hematite and hydrated hematite. Some replacement in adjoining greenstones and tuffs by the same solutions may also have taken place, but the latter occurrences may represent replaced iron formations originally bedded in with the volcanics. Iron formation in the same relationship to volcanics is extensively developed on the western Menominee Range of Michigan, in the Middle Huronian belts; also appears in similar relations on the Vermilion Range; and is abundantly exposed in the same stratigraphic position no farther away than the southeast arm of Steep Rock Lake itself. Furthermore, the writer's classification of drill cores, made June 11, 1938, on the prop¬erty, contains the following, for hole 8, in the original strike of the A ore body: "332-342 ore; 342-350 much-leached sugary chert with thin ferruginous slate bands." This is a typical iron formation. The ore in this first group of holes (Numbers 6 to 13, incl.) is described in the writer's 1938 notes as follows: "The ore is hard, massive hematite with some limonite, and shot through with many small vugs." The breccia forms in the float ore and in the drill samples were also noted. As a field classification this does not check badly with Professor Schwartz's microscopic work. Notes supplied by Mr. Neeland, then geologist at the exploration, show: "Hole 23 has some iron formation, not logged yet." It appears therefore that there is some iron formation at the exploration, much iron formation in similar stratigraphic position in the vicinity, and iron formation similarly located as to volcanics on the Vermilion and western Menominee Ranges. Certain of the holes, notably Holes 25 and 27, showed some specular hematites resembling those known to be formed from cherty iron formation elsewhere. Hence the writer concludes that at least a small part of the Steep Rock ores results from replacement of iron formation. By far the greater part of it is, as the authors say, clearly a replaced limestone and dolomite breccia, with the breccia outlines still preserved in much of the ore, and all of the replacement is by hot ascending waters. The authors' citation of the neighboring Atikokan pyrite, pyrrhotite and magnetite

Jan 1, 1943

By Norris Johnston, Carrol M. Beeson

The gravimetric-vacuum distillation method was developed to permit rapid and accurate determinations of the oil-water ratios of small samples or sands containing little oil. In addition, the samples usually are so well cleaned and so little altered by the distillation at reduced pressure that rapid estimations of other physical properties may be made with the evacuated cores. Requiring only elementary glass-blowing technique, the distilling tubes and traps used in determining oil-water ratios were easily fashioned from the usual glassware. A sketch and description are given of the necessary apparatus, including the cylindrical electrical heaters. The procedure, requiring about 40 min., consists in raising the temperature and maintaining it between 675' and 725°F. for at least 10 min. while the pressure is held between I and 2 mm. Hg. The fluids condensed in the trap (cooled by a mixture of kerosine and solid carbon dioxide) are separated in a centrifuge and the volume of water is recorded. Determination of changes in weight with an analytical balance of all parts of the apparatus permits computation of weight of oil distilled and total weight of oil recovered. Introduction In determining the oil-water ratios of core samples, distillation at atmospheric pressurel-5 has proved to be sufficiently reliable for samples containing moderate quantities of oil. Since small samples and sands with little oil are encountered, how- ever, it appeared advisable to develop a method that would be applicable under these circumstances. Thegravimetric-extraction procedure1,6-9 undoubtedly is very reliable and could be used in all tests, but the time consumed in the determination would often delay field operations. This would be especially true when dealing with tight sands or viscous oils, both of which retard the extraction process. Accordingly, the gravimetric-vacuum distillation method was developed in order to combine the good features of both of the older methods; that is, accuracy and speed. By reducing the pressure, it was found possible to perform the distillation at a temperature that permits the use of glass apparatus, all parts of which can be weighed on an analytical balance. Thus, the fluids may be removed quickly from the core, the water is readily trapped and measured, and the loss in weight of the core is easily determined. In addition, the total weight of material condensed in the distilling tube and in the trap provides a method of determining the oil-water ratio that is practically independent of the one involving the loss in weight of the sample. The use of vacuum not only permits as much accuracy as does the gravimetric-extraction process, but it actually allows an increase in speed over the atmospheric-distillation method, because of the time required to cool the metal pots from about 1200°F. between runs. More important yet, the innovation makes possible the almost immediate reporting of permeability, and saturation, which is impossible

Jan 1, 1946

By Norris Johnston, Carrol M. Beeson

The gravimetric-vacuum distillation method was developed to permit rapid and accurate determinations of the oil-water ratios of small samples or sands containing little oil. In addition, the samples usually are so well cleaned and so little altered by the distillation at reduced pressure that rapid estimations of other physical properties may be made with the evacuated cores. Requiring only elementary glass-blowing technique, the distilling tubes and traps used in determining oil-water ratios were easily fashioned from the usual glassware. A sketch and description are given of the necessary apparatus, including the cylindrical electrical heaters. The procedure, requiring about 40 min., consists in raising the temperature and maintaining it between 675' and 725°F. for at least 10 min. while the pressure is held between I and 2 mm. Hg. The fluids condensed in the trap (cooled by a mixture of kerosine and solid carbon dioxide) are separated in a centrifuge and the volume of water is recorded. Determination of changes in weight with an analytical balance of all parts of the apparatus permits computation of weight of oil distilled and total weight of oil recovered. Introduction In determining the oil-water ratios of core samples, distillation at atmospheric pressurel-5 has proved to be sufficiently reliable for samples containing moderate quantities of oil. Since small samples and sands with little oil are encountered, how- ever, it appeared advisable to develop a method that would be applicable under these circumstances. Thegravimetric-extraction procedure1,6-9 undoubtedly is very reliable and could be used in all tests, but the time consumed in the determination would often delay field operations. This would be especially true when dealing with tight sands or viscous oils, both of which retard the extraction process. Accordingly, the gravimetric-vacuum distillation method was developed in order to combine the good features of both of the older methods; that is, accuracy and speed. By reducing the pressure, it was found possible to perform the distillation at a temperature that permits the use of glass apparatus, all parts of which can be weighed on an analytical balance. Thus, the fluids may be removed quickly from the core, the water is readily trapped and measured, and the loss in weight of the core is easily determined. In addition, the total weight of material condensed in the distilling tube and in the trap provides a method of determining the oil-water ratio that is practically independent of the one involving the loss in weight of the sample. The use of vacuum not only permits as much accuracy as does the gravimetric-extraction process, but it actually allows an increase in speed over the atmospheric-distillation method, because of the time required to cool the metal pots from about 1200°F. between runs. More important yet, the innovation makes possible the almost immediate reporting of permeability, and saturation, which is impossible

Jan 1, 1946

By H. I. Meyer, D. F. Searcy

INTRODUCTION The analysls of our previous paper' on the behavior at two immiscible fluids separated by gravity into two dlstinct saturated zones in the porous medium was shown to be theoretically valid only if one of the two fluids was immobile. The practical problems associated with flow of both phases have so far been impossible of solution by these analytic methods. We, therefore, decided to resort to a simulator study to answer the following pertinent questions: 1. If the lighter fluid is produced from a point above the fluid-fluid interface, how long will it take for the heavier fluid to come up to the point where production of both fluids is taking place? 2. After steady-state two-phase production is established, what is the relative production rate of each phase, on what physical variables does this depend, and what are the boundary conditions at the outflow face? 3. A third question was at least partially answered in the course of this investigation: that of the shape of the interface under flow conditions. These questions are of fundamental importance in the fields of hydrology and the reservoir mechanics of oil and gas production. In order to simplify equipment used and still retain a fair physical representation of these phenomena, it was decided to use a Hele-Shaw type of analogy in which the flow took place between two vertically mounted pieces of plate glass. The advantage of this system is that it eliminates any surface effects between the matrix of the porous medium (e.g. packed sand) and also allows equilibrium conditions to be established more quickly. The principle disadvantage (apart from the obvious one of being one more step removed from the prototype) is that our equipment limited us to two dimensional flow studies. In spite of these limitations answers to the questions were obtained which seem adequate for our purposes. We would like to see more work of this nature done to verify and to improve our conclusions. DESCRIPTION OF EQUIPMENT AND PROCEDURE A drawing of the equipment used in this study is shown in Fig. 1. Fluid flow takes place between the two 36 in. x 12 in. pieces of plate glass held apart at the long edges by two spacers of cellulose acetate sheet (Kodapac IV) which is available in several thicknesses. This sandwich was clamped together by small c-clamps whose stress was distributed by long pieces of 3/8-in. keystock. Accurate spacing was obtained by tightening these clamps as indicated by micrometer measurements on the outside of the glass. At the upstream end of the plates a piece of 6-in. diameter pipe simulated an infinite reservoir, while at the downstream end a 2-in. Lucite cylinder with a small hole near the top of the flow region served to drain the fluid. Sealing was achieved by O-rings, the whole system being tightened by pressure on the Lucite tube provided by set screws (not shown in the drawing). The total head

Jan 1, 1957

By Frank Marotta, Louis B. Lesem, Frank Greytok, John J. McKetta

Although one of the primary variables in the calculation of the flowing bottom-hole pressure in gas wells from surface measurements is the temperature at any point and its distribution in the flow-string, only few experimental data are available in the literature and little attention has been given to analysis of the problem. Virtually all of the recently published methods of calculating flowing bottom-hole pressures depend on the assumption that either the temperature is constant at some average value or that the variation is linear with depth. The purposes of this work are to analyze the problem theoretically and to verify the analysis by comparison with experimental data so that practical problems in the analysis of the behavior of gas wells can be solved with greater accuracy, reliability, and ease. MATHEMATICAL OUTLINE OF PROBLEM Assuming that: 1. The mass velocity and chemical composition of the gas stream are constant and in normal gas well operations, the change in linear velocity in the entire flow-string is trivial, 2. The product of the density and heat capacity of the gas is constant, 3. No horizontal temperature gradient exists in the gas stream, 4. Net flow of heat by conduction within the formation and in the gas stream in the vertical direction is trivial in magnitude and can be neglected, 5. The regional vertical geothermal gradient is constant, and 6. The temperature of the gas entering the borehole is constant, and equal to that of the reservoir, a set of two simultaneous, linear partial differential equations with appropriate boundary conditions was derived to describe the temperature distribution in the gas stream and the surrounding formation. These equations were solved by operational techniques for the distribution of temperature in the gas stream. The resulting integrals were evaluated numerically on an IBM 604 at the Machine Accounting Div. of the Railroad Commission of Texas. DERIVATION OF FUNCTIONS FOR THE DISTRIBUTION OF TEMPERATURE The physical system is a circular hole of radius a in an infinite medium with thermal conductivity K, density p8, and heat capacity c,. Under shut-in conditions the well is in thermal equilibrium with the surroundings and the increment in temperature is given by - ?T3/L x. Gas of density pg and heat capacity c.. flows upwardly through this hole in the direction of increasing x with a linear velocity W. Writing a heat balance on an element of gas ?x in thickness, convective heat transfer + conductive heat transfer + energy required to lift a unit mass of fluid = change in energy content. pa2W po Co To - pa2Wpo Co To x+xx - 2apK?x ?T8/?r r=a - Wpa2 po?x/778 = CoPopa2?x?To/?t... Dividing by (copopa2?x) and taking the limit as ?x tends to zero, -W (?To/?x + 1/778Co) + 2 K/a Po Co ?T3/?r r=u = ?To/?t

Jan 1, 1958

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to I700°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid,i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By T. J. Fabiniak, R. A. Dodd, R. Balow

ALTHOUGH the (111) slip direction in pure bcc metals is well established, the information on operative slip planes is less unambiguously interpreted. So far, (110) {112), and (123) slip planes have been identified, but it is not certain whether glide on (112) and (123) really occurs or if it is composite slip on non-parallel (110) planes. The second of these possibilities is supported by the work of Chen and Maddin on niobium and molybdenum, and a subsequent analysis by these same workers of slip in bcc metals generally.3 The alternative possibility is exemplified by the work of Opinsky and smoluchowsky4 who concluded that slip in Fe-Si crystals can occur on any one of the systems {110}(111), {112}(111), and {123)(111), depending on which system the resolved shear stress is highest. Allen et alS5 also found that glide in ar iron could occur on any of these three systems, the operative system being determined principally by orientation. By an analysis of crystal rotation, slip lines, and X-ray asterism Harris6 concluded that niobium also deforms on these same systems, but if one of these glide planes does not coincide with the plane of maximum resolved shear stress, composite slip on nonparallel (110) planes may occur giving a macroscopic high indices slip plane. Earlier work on iron by Vogel and Brick reached the same conclusion.7 The analysis of slip in bcc metals is made more difficult by the fact that the slip lines may be quite wavy. In fact, the generality of wavy slip lines suggests that screw dislocations slip readily from one plane to another in the (111) zone ("pencil glide") although, as noted, it is not certain whether planes other than (110) really contribute to the slip. If planes of higher indices than {110} do operate, there is a possibility they may do so more readily at higher temperature Argon and Maloof9 observed {100}{211}(111) slip in tungsten single crystals plastically strained at low temperatures, but the results were interpreted in terms of an orientation-dependence rather than temperature-dependence. Therefore, at the present time corroborative evidence for the operation of higher indices slip planes at higher temperatures is lacking. The present results were obtained during the course of an investigation into the effect of cathode and anode surface crystallography on the prebreakdown currents of vacuum insulated devices. In the experiment of particular interest, the 1/8-in.-diam anode and the in.-diam cathode were tungsten crystals (total impurities -230 ppm) with (110) and (100) faces respectively. The faces were electrolytically planed and examined for initial perfection by plastic/carbon replicas and a study of Kikuchi lines in reflection electron diffraction patterns. They were aligned precisely parallel in an insulating holder incorporated into the electron microscope, the measured microscope vacuum being 2 x 10-5 torr, and the electrode spacing 0.01524 cm. The anode structure shown in Fig. 1 was obtained

Jan 1, 1970

By G. S. Scott, G. W. Jones

ECONOMIC waste caused by mine fires may become considerable,15 especially if a fire is allowed to spread or temporarily to get beyond control. It is important, therefore, to act promptly whenever a fire is suspected and to make every action count. To contribute toward its extinction effectively it is necessary to know at the earliest possible moment, and continuously thereafter, what is happening at the seat of the fire, which may be in a remote or inaccessible area, and also to recognize what may be expected as a result of any proposed combative measure. In combatting a fire the mining engineer and the chemist should cooperate, first deciding upon the course of action to be taken and then drawing upon the mining engineer's intimate knowledge of the physical structure of the fire area, the cost and time required to carry out proposed operations, and the probable efficiency with which these operations could be performed, and upon the chemist's knowledge for the results to be expected therefrom. After the initial steps to be taken have been decided, it devolves upon the mining engineer to see that they are carried out and upon the chemist to evaluate the results and to keep the mining engineer continuously informed in regard to a variety of matters-such as the composition and toxic or asphyxiating properties of the atmosphere in which the men may be working, whether the fire is increasing or decreasing in intensity and its probable temperature, the quantity of air leakage and the explosion hazards of the fire area. The purpose of this paper is to discuss what the chemist can and cannot contribute as a member of the fire-fighting personnel. The technical literature contains several hundred papers relating directly and indirectly to mine fires, and this fact alone is testimony to the complex nature of the phenomena involved in the birth, life, and final demise of a fire. A fire may be stopped (I) by preventing oxygen from reaching the coal or (2) by removing the conditions necessary for the rapid reaction of coal with oxygen; i.e., decreasing the temperature. All methods of prevention or control. necessarily must be based upon one or the other, or both, of these two principles. . The chemistry of a fire may be understood readily if the low-temperature oxidation of coal is considered as a starting point; then oxidation at higher temperatures (or combustion) ; and with these, the composition of the solid and gaseous products resulting from the oxidation or from the effects of the heat liberated. This discussion refers particularly to Pennsylvania anthracite, although much of the material applies equally well to coals of lower rank. OXIDATION OF COAL Oxidation of coal fundamentally is confined to the surface; that is, the rate at which oxygen penetrates into the interior of a solid block of coal is so slow that it may be ignored.6,16 Oxidation starts when a fresh surface is exposed, and the rate is

Jan 1, 1942

By Martin S. Maier, H. R. Nelson

THE diffusion of metals plays an important role in many metallurgical processes, 1,2 as, for example, the formation of alloys by the annealing of mixed powders, the homogenization of segregated alloys, and the carburization of steel. Other equally important phenomena, such as recrystallization and creep, are based on the movement of like atoms. Although much is known concerning the effects of diffusion in metals, very little is known concerning the details of the physical processes involved.1,3-5 The data that should give most information concerning the processes involved in diffusion are those on the diffusion of like atoms-self-diffusion. Very little is known concerning the rates of self-diffusion of metals because before the discovery of artificial radio-activity in 1934 there was no means of detecting the movement of the diffusing atoms through the solvent metal except in the elements possessing natural radioactive isotopes-lead, thallium and bismuth. Using the induced radioactivity of the element as an indicator, atoms can now be "tagged" so that the rate of diffusion of the radioactive isotopes of an element (tagged atoms) into the stable isotopes of the same element can be measured. As the radioactive and stable isotopes of an element differ only in nuclear structure, it is quite certain that all isotopes of an element diffuse at the same rate. Two techniques have been used to measure self-diffusion. In one, a thin layer of radioactive metal is deposited on the face of the solvent metal, and the decrease in the surface activity as the radioactive atoms diffuse into the solvent metal is measured. This method has been used to determine the coefficients of self-diffusion of lead6-10 and bismuth10 using natural radioactive isotopes, and of gold11 and copper12 using artificial radioactive isotopes. In the other technique a thin layer of the radioactive metal is deposited on one face of the solvent metal, and after diffusion has occurred the specimen is cut in thin sections to obtain the concentration-penetration curve. This method has been used to determine the coefficients of self-diffusion of gold,13 zinc, 14-16 silver,17 and copper.18 The second method was used for the work described in this paper. MATERIALS The coefficients of self-diffusion were determined in two grades of polycrystalline copper and in single crystals of copper. Commercial OFHC copper was used in the form of disks I in. in diameter by 1/8 in. thick. Samples of high-purity copper described by Phillips and Skinner19 were supplied through the courtesy of the American Smelting and Refining Co. The high-purity copper rod was used without remelting by cross-rolling to a thickness of 0.075 in., from which disks 7/8 in. in diameter were cut. A good grade of bus-bar copper was used to make the single crystals.

Jan 1, 1942

By P. B. Crawford, W. L. Huskey

A study has been made to determine the effects of random vertical fractures existing in a reservoir matrix on the effective matrix properties and producing characteristics of a well. The study indicated that short vertical fractures may distort the isopotentials by 1 percent in the vicinity of the fracture. A correlation was developed which showed the effect of fracture density on the producing capacity of a well. The correlation indicated that fracture shape had little effect on producing capacity, but that total fracture length was closely correlated with the producing capacity. Effective values of reservoir permeability were found to correlate closely with fracture density when measured parallel to the direction of flow. INTRODUCTION In reviewing the petroleum literature, it is found that in most analytical solutions of hydrocarbon reservoir behavior the assumption is made that the rock is uniform throughout although core analysis and well logging surveys indicate that substantially all reservoirs are heterogeneous and some are fractured. Only in recent years have investigators studied the effects of reservoir hetrogeneity. Russell1 discussed the effect of fractures in reservoirs. The literature indicates that fractures greatly affect the exploitation of man reservoirs. This is described by Elkins and Skov2 and Little-field et al. 3 Several types of reservoir heterogeneity have been studied by unsteady-state methods. In 1959, Landrum et al. 4 showed that transient phenomena in hydrocarbon reservoirs could be studied by thermal models. pickering5 studied the flow of heat in stratified linear reservoirs consisting of plates of different metals separated by sheets of rubber which were suddenly exposed to a low-temperature source at one end. Cotman6 studied both laterally and vertically heterogeneous thermal model reservoirs with special reference to cross flow. Another type of reservoir heterogeneity involves the presence of highly permeable, circular lenses around or near the wellbore which was studied by Miesch7 using a thermal and a steady-state model. Many studies have been made of the effects of induced hydraulic fractures on well performance. 8-10 Work regarding vertical fractures that exist initially in the reservoir was reported by Givens, et al.11 Since there appears to be little published work on the importance and influence on reservoir performance of fractures that exist out in the rock matrix, this study was conducted to determine the effects of vertical fractures on pressure distribution, producing capacity and the effective permeability of the reservoir rock. The analogy between the flow of electrical current through a conducting body and the flow of fluid in a porous medium provides a convenient method of studying various aspects of petroleum reservoirs. For electrical radial steady-state flow,12 For steady-state fluid flow, With the above analogy, it is only necessary to establish the ratio of the values of the electrical units in terms of the corresponding flow units to make the analogy quantitative. The ratios are shown below.

By A. Dubé, G. Letendre, C. E. Beaulieu

An experimental study has been made of the time dependence of internal .friction and modulus of rigidity in- freshly quenched steels at room temperature. The effects of frequency, composition, and various thermal treatments are given. The kinetic 1aws observed cannot be fully explained by the so-called first stage of tempering and the transformation of retained austenite. It is suggested that the observed phenomena are due to the progressive immobilization of dislocations introduced by the martensitic transformation. It is generally agreed that the conversion of tetraginal martensite into cubic ferrite and ce-mentite occurs in three stages which at moderate rates of heating take place in the following temperature ranges:'-3 a) The first stage involves mainly a partial loss of tetragonality of martensite and the formation of ?-carbide between 95" and 175oC. b) The second stage consists of the decomposition of retained austenite between 230 and 290' C. c) The third stage covers the formation of ce-mentite between 290o and 400' C. The kinetic laws of these heterogeneous reactions have also been the subject of isothermal studies. Thus, Roberts, Averbach. and cohen3 report a very low reaction rate with a eutectoid steel at room temperature. For example, less than 10 pet of the contraction associated with the first stage is observed after 50 hr at room temperature. Hollonlon, Jaffe, and Buffum4 show that under the same conditions less than 10 pet of the tetragonality is lost. These results have led to the belief that martensite is a relatively stable phase at room temperature. On the other hand, it is well known that important structural changes occur in martensitic steels during the first few minutes at room temperature after quenching. This pretempering has at least two important consequences. In the first place, freshly quenched steels have a tendency to crack at room temperature, a fact which leads to the necessity of tempering as soon as possible after the quench. Another important consequence of pretempering a steel for short periods of time at room temperature is the stabilization of the retained austenite. Thus, as shown by Cohen,5 a very pronounced stabilization is effected with holding periods of 30 min at room temperature. Since these two effects are apparently not caused by the heterogeneous reactions mentioned above, they must be related to the rearrangement of structural defects within the martensite and retained austenite. According to the modern theory of dislocations, the shears required to effect the austenite-marten-site transformation may be realized through the motion of dislocations at the austenite-martensite interface and within the martensite plates.6 In this way, a martensitic transformation closely resembles a plastic deformation. In cold-worked solids, high concentrations of dislocations are left immediately after the plastic deformation and it seems reasonable to assume that appreciable densities of dislocations should also appear in the wake of a martensitic transformation. A considerable part of the high hardness of martensite would then originate in the obstruction of dislocations in analogy

Jan 1, 1961

By W. Mckewan, W. M. Fassell

The oxidation rates of copper have been determined at temperatures from 600" to 900°C in oxygen from 14.7 to 400 psi total oxygen pressure. The oxidation rate of copper is unchanged by oxygen pressures within the range studied. The observed data extend Feit-knecht's conclusion concerning the pressure independence of copper from atmospheric pressure to 400 psi. All samples studied in the above-mentioned temperature and pressure range have both Cu2O and CuO present in the oxide film. NUMEROUS papers have been published on the oxidation of copper, some of which have noted the effect of oxygen pressure on the oxidation rate of copper. It must be noted, however, that no data on the oxidation rates of copper at pressure in excess of 1 atm have been reported in the literature. (Le Chatelier¹ reported that a black oxide of silver was formed at 300°C and 15 atm pressure.) This is likewise true for the other metals. This investigation was initiated to obtain experimental oxidation rate constants for pure metals at elevated temperatures and high oxygen pressure. Copper was selected as the first metal since probably more reliable data are available on its oxidation rates and related physical and chemical properties than for any other metal or alloy. As a general summary, the following conclusions appear well established for the oxidation of copper: 1—The oxide coating consists of Cu2O with a superficial coating of CuO providing the ambient oxygen pressure exceeds the equilibrium pressure for the coexistence of Cu2O and CuO.² The following sequence of phases is then Cu/Cu2O/CuO/O2 (gas). The Cu2O consists of large crystals that have no relation to the orientation of the metal crystals, except for a very thin layer adjacent to the metal." The CuO consists of very fine crystals randomly oriented. If the oxygen pressure is below the equilibrium pressure for the coexistence of Cu2O and CuO, the coating consists of Cu,O only. 2—The rate-determining factor in the parabolic oxidation of copper is the diffusion of Cu+ ions through the Cu,O layer.4,6,7 The Cu+ ions are accompanied by electrons to maintain electrical neutrality. The mechanism of the reaction at the Cu2O/CuO interface and the method of growth of the CuO is in some doubt. 3—On copper, there are three reported pressure effects: (a) At pressures below 0.3 mm Hg oxygen pressure, the oxidation rate increases directly with pressure.', ' .Vxygen starvation at the surface may account for this effect. (b) At oxygen pressures from 0.3 to 63 mm, the oxidation rate increases as the 7th root of the oxygen pressure providing the temperature is such that only Cu2O is present in the film. (c) At pressures from above the equilibrium pressure for the coexistence of Cu2O and CuO (varies with temperature) to atmospheric pressure, the oxidation rate is independent of the oxygen pressure.' Equipment In order to determine the oxidation rates of metals in an oxidizing atmosphere at pressures up to 400 psi, the equipment is somewhat different than for low pressure work as is shown in Figs. 1 and 2. A Leeds and Northrup Micromax recording controller (A) is used to control the temperature of the Ni-chrome furnace winding in conjunction with a Micromax electric drive unit. The drive unit adjusts a 20 amp Variac (variable transformer) to control the power input into the Nichrome furnace winding. Due to the "self heating" of the sample by oxidation, frequently encountered in oxidation rate studies, it is essential that the sample temperature be measured independently. This is done by means of a series of six chromel-alumel calibrated thermocouples located spirally around the oxidizing metal sample. Each thermocouple is partially shielded from the direct radiation of the furnace wall by

Jan 1, 1954

By Edward E. Hicke, Charles A. Stickels

The dihedral angle of liquid-lead inclusions in solid nickel has been measured as a function of temperature from 371 to 816 C at zero pressure. and as a function of pressure up to 50,000 psi at 317 and 593 C. Thermodynamic expressions are derived for the temperature and pressure coefficients of interfacial tensions in this system. A method is presented for obtaining relative tempmature and pressure coefficients from dihedral-angle data, and the resulting values are used in conjunction with the thermodynamic relations to calculate excess properties of the solid-liquid interface. Defining the position of the solid-liquid interface by the condition that the excess concentration of lead is zero, the excess concentration of nickel and the excess entropy at the solid-liquid interface are: where y(593) is the interfacial tension of the nickel grain boundary saturated with lead at 593C and zero pressure. These values are considered reliable to within a factor of two. While similar calculations are not possible for the nickel grain boundary, it is shown that the expwimental results imply that the excess concentration of nickel at the boundary and the excess entropy of the boundary are negative. THE temperature and composition dependencies of interfacial tensions in metal systems have been reported by several authors in the last 15 years.'-' No measurements of the effect of pressure on inter- facial tensions in metals have been reported, although measurements made on nonmetallic gas/liquid and liquid/liquid systems suggest that a measurable effect should exist.6-l2 The purpose of these experiments was to determine the influence of temperature and hydrostatic pressure on dihedral angles in the Pb-Ni system. The equilibrium dihedral angle is expressed as a ratio of interfacial tensions by2: where 8 is the dihedral angle, yGB is the Ni-Ni grain boundary tension, and SL is the solid Ni-liquid Pb interfacial tension. Three sets of ex- periments were run to determine: a) the effect of temperature from 371" to 816°C on the dihedral angle at zero pressure; b) the effect of pressure up to 50,000 psi on the dihedral angle at 371° and 593°C. THERMODYNAMICS The properties of interfaces of most direct concern are the interfacial tension, excess concentrations of various components at the interface and the excess entropy of the interface, S°. These quantities are defined following Gibbs. Consider an interface separating phases a and 0. Construct two surfaces C, and C such that all properties of phase a remain uniform up to C, and all properties of phase 0 remain uniform up to C. The region between C, and Cp is the interfacial region. Let a "dividing surface", D, be constructed in the interfacial region such that it passes through all points "similarly situated with respect to the condition of the adjacent matter."l3 Surface D divides the interfacial region into a portion a' adjacent to phase adjacent to phase . Let a closed curve, C, enclose an area A in D. Erect normal lines to D along C; these lines and the surfaces C,, Cp, and D then enclose volumes V and V' in the two halves of the portion of the

Jan 1, 1964

By J. C. Uy, A. A. Burr

IN the primary solid solutions of zirconium-base alloys, there is a striking regularity of the effect of solute valence on the stabilization of the allotropic phases.1 The valences derived by pauling2 are for elements as they are bonded in the solid metallic state. Effects of variations in isotopes, alloying elements, and allotropes on their valences are difficult to determine and such data are presently unavailable. Pauling's values are somewhat empirical and approximate, but if some definite correlations can be found between those values and experimental observations, this will lend support to the tacit assumption that the possible variations in valence mentioned above are small. Pauling has amassed a large amount of evidence of such correlations. It is the purpose of this technical note to show another application of the Pauling valences and to offer a possible explanation for this observation. The relationship between the Pauling metallic valence of the solute and the stabilization of allotropic phases in zirconium is shown in Table I, which has been compiled from available data in the literature3 plus the results of work done at Rens-selaer Polvtechnic Institute.' The chemical valences are included for comparison. It can be seen that a solute whose metallic valence is lower than that of the solvent tends to stabilize the a phase while one whose metallic valence is higher than that of the solvent tends to stabilize the 0 phase. It should be noted that, inasmuch as the Pauling valences are periodic with atomic number, this is tantamount to saying that the elements in groups I-A, 11-A, III-A, III-B, IV-B, V-B, and VI-B are a stabilizers while those in groups IV-A, V-A, VI-A, VII-A, VIII-A, I-B, and 11-B are ß stabilizers. The chemical valences do not show such consistency. Although the zirconium-rich end of the Zr-Au diagram is not available, it call be expected that gold, having a metallic valence of 5.56, would stabilize the ß phase. At absolute zero, the Fermi energy level is the criterion of equilibrium, i.e., the structure having the lower Fermi level will be more stable. Conse- quently, allotropic transformation occurs in a metal when thermal excitation raises the Fermi level to a point at which the atoms can be better accomodated by a different structure which yields a lower Fermi level.4-6 Thus in allotropic transformation, a change in structure occurs as a result of the change in the energies of the bonding electrons. Since the Pauling valence is the number of bonding electrons per atom, and these are the only electrons whose energies are affected by thermal excitation,* it can be inferred that the introduction of a solute which has a higher Pauling valence than that of the solvent raises the initial Fermi level; consequently, the transformation temperature is lowered. The converse is also true. The fact that at the transformation temperatures this statement is still fairly valid implies that the contribution due to the difference in specific heat terms of the two allotropes is comparatively small.

Jan 1, 1962

By Walter Bonsack

THE CHAIRMAN.-This is the third and last session of the Institute of Metals Division's Symposium on Secondary Metals, and certainly the best of those that I have attended in the last few years. I would say that the increase in interest in secondary metals is quite noticeable by the steadily increasing attendance at these meetings. We have heard about the necessity of utilizing salvaged materials, but we still speak about them as low-grade, or down-graded materials. We still have the wrong perspective. We must willingly admit that these materials are valuable; we cannot go on using the choicest primary metals as morsels for our economic diet in a war of such unbelievable dimensions. This brings up the question-why are we so selective. The answer certainly is not that we know nothing else will do, but rather that we do not know what else will do. To be honest, we should admit our lack of knowledge concerning our complex alloys. Compared to the organic chemists, we metallurgists are very conservative, and the sooner we realize this and start to overcome it the better, because if we do not eliminate this difference, many customers of the metals business will go over to the plastics. If we take for example the development of aluminum alloys, you will see what I mean. From the binary aluminum alloys of 1920, we have progressed to ternary and quarternary alloys in the 1930's. We are only now beginning to use more complex alloys as we are forced to learn more about the effect of various elements on existing alloys. The effects of these elements should be studied now. They can be studied by two methods of approach. The usual method is to start from the base alloy and add various elements one by one in increasing amounts and study the resultant changes in properties. This is a tedious, long way. The other method which the smelters frequently use is to take the off-grade heats and study their characteristics. While the producer of primary alloys often has difficulties in alloying certain elements with the alloy under investigation, the smelter often finds them well alloyed in his raw materials and has no difficulties at all. Elements such as lead are difficult to alloy with aluminum and they tend to segregate severely. However, the amount which will remain alloyed in the metal is usually found in some "secondary" aluminum alloys. If one considers such concentration as the saturation, then by dilution with the same type of alloy, but free of such element, one can produce numerous intermediary alloys for investigation. In this fashion one is fairly certain to get uniformly spaced concentrations of the element under investigation. Similar cases probably exist with other metals. Nevertheless, the amount of work necessary to study all possible combinations is still tremendous. Necessity forces us now to utilize alloys which contain more elements than we are accustomed to. It is, therefore, necessary to study carefully the more complicated alloys. In secondary aluminum we are working and using the alloys which contain as many as 6 to 10 elements and we have learned over a period of several decades to balance

Jan 1, 1943

By W. T. Bishop, G. A. Crowe

While the literature in the United States on general polarographic technique is extensive, very little appears to be directly applicable to the analysis of flotation tailings. For this reason, it seemed worth while to present a few polarographic methods of ore analysis that have been in constant use in the laboratories of the Hercules Experiment Station for the past few years. At the time of our initial investigation of the polarographic method, there was little or no mention of its specific application to flotation tailings. It was therefore necessary for us to establish suitable conditions for the analysis of our flotation tailings and to consider possible interfering constituents. The polarograph, or dropping mercury electrode, method was discovered in 1925 by J. Heyrovsky and M. Shikata,1 of the Charles University, Prague. This method has since received extensive development and the literature contains many articles on the use of the polarograph for the quantitative determination of metals as well as anions, oxygen in solution, and reducible organic compounds. Kolthoff and Lingane,² by the publication of their book, "Polarography," in 1941 did much to advance the knowledge and use of the polarograph. In chapter 25 of that book, methods for the polarographic analysis of brass, steel and iron products, alloys, and zinc ore are given. Aluminum,³ cadmium,³,4 cobalt,4 cop-per,³-9 gold,10 iron,3,11 lead,³,l2,l³ molybdenum,14 nickel,4,8,9 tin," and zinc³,4,5,7 in ores have been analyzed by the polarograph. However, most of the work on tailing samples has been published in Russian journals and translations are not yet readily available. In this paper we will describe the method that was developed and used in our laboratory for the determination of copper, zinc, and lead in flotation tailings. Principle OF the Method The polarograph is an instrument for applying a potential to a mercury pool and a dropping mercury electrode separated by a solution, and for measuring the resultant electrical current. The procedure is essentially a small-scale electrolysis, in which the voltage required to reduce or oxidize the material identifies it qualitatively and the current measures the concentration quantitatively. Different constituents in a sample may often be determined simultaneously provided they reduce at sufficiently different voltages. An example is the determination of copper and zinc in the same solution. The reduction potentials are quite far apart, as shown in Fig. I. The polarographic method is particularly useful in the range of concentration between those normally determined by spectographic and chemical methods. In

Jan 1, 1947

By G. A. Crowe, W. T. Bishop

While the literature in the United States on general polarographic technique is extensive, very little appears to be directly applicable to the analysis of flotation tailings. For this reason, it seemed worth while to present a few polarographic methods of ore analysis that have been in constant use in the laboratories of the Hercules Experiment Station for the past few years. At the time of our initial investigation of the polarographic method, there was little or no mention of its specific application to flotation tailings. It was therefore necessary for us to establish suitable conditions for the analysis of our flotation tailings and to consider possible interfering constituents. The polarograph, or dropping mercury electrode, method was discovered in 1925 by J. Heyrovsky and M. Shikata,1 of the Charles University, Prague. This method has since received extensive development and the literature contains many articles on the use of the polarograph for the quantitative determination of metals as well as anions, oxygen in solution, and reducible organic compounds. Kolthoff and Lingane,² by the publication of their book, "Polarography," in 1941 did much to advance the knowledge and use of the polarograph. In chapter 25 of that book, methods for the polarographic analysis of brass, steel and iron products, alloys, and zinc ore are given. Aluminum,³ cadmium,³,4 cobalt,4 cop-per,³-9 gold,10 iron,3,11 lead,³,l2,l³ molybdenum,14 nickel,4,8,9 tin," and zinc³,4,5,7 in ores have been analyzed by the polarograph. However, most of the work on tailing samples has been published in Russian journals and translations are not yet readily available. In this paper we will describe the method that was developed and used in our laboratory for the determination of copper, zinc, and lead in flotation tailings. Principle OF the Method The polarograph is an instrument for applying a potential to a mercury pool and a dropping mercury electrode separated by a solution, and for measuring the resultant electrical current. The procedure is essentially a small-scale electrolysis, in which the voltage required to reduce or oxidize the material identifies it qualitatively and the current measures the concentration quantitatively. Different constituents in a sample may often be determined simultaneously provided they reduce at sufficiently different voltages. An example is the determination of copper and zinc in the same solution. The reduction potentials are quite far apart, as shown in Fig. I. The polarographic method is particularly useful in the range of concentration between those normally determined by spectographic and chemical methods. In

Jan 1, 1947

By O. B. Hopkins

There was no noteworthy development in the oil industry in Peru during 1933 and all activities were restricted to the producing fields. The output of the country increased above that of previous years but there still remained a substantial shut-in production at the close of the year. The total production during 1933 is estimated at 13,259,891 bbl., of which the International Petroleum Co., Ltd. contributed 11,205,-362 bbl. A relatively small amount of new drilling was undertaken during the year. The International completed only one new well although a number of the old producers were reworked and deepened. Comments on Tables There are four oil districts in Peru, as shown in Table 1, although only three of these are now being operated. The exhausted Pirin field was abandoned eight years ago. La Brea-Parinus.—The La Brett-Parinas fields are on the property of the International Petruleum Co., Ltd. in the westernmost part of Peru. These fields include a number of producing districts that are defined by complex fault blocks associated with anticlinal folds. Data covering all the items listed in the table are not available on these fields but can perhaps be supplied in part in the future. Lobitos and Restin.—These two fields belong to the Lobitos Oilfields Limited and are near the coast, 10 to 20 miles north of the La Brea-Parinas fields. According to the Department of Mines and Petroleum of Peru, 311 wells at Lobitos and 197 at Restin had been drilled to the end of 1927. Since that date there has been enough drilling to increase moderately these figures. The depth of wells is not available but it is believed that their average depth is slightly greater than in the La Brea-Parinas area. The productive horizons are of Eocene age. zorritos.—The Zorritos field is the northernmost in Peru and is operated by the Establecimiento Industrial de Petroleo de Zorritos. The field is on the coast about 70 miles north of Lobitos. The number of wells drilled in this field to the end of 1927 was 343, according to the Department of Mines and Petroleum of Peru. The depths of these wells are reported to range from 300 to 700 ft. The largest wells do not produce

Jan 1, 1934

Discussion of the paper of PHILIP W. HENRY, presented at the New York meeting, February, 1915, and printed in Bulletin No. 97, January, 1915, pp. 23 to 30. C. ,E. GRUNSKY, JR., San Francisco, Cal. (communication to the Secret ary*).-The difference of opinion of engineers on the subject of depreciation is justified, to some, extent, by the many viewpoints from which such a subject can be considered when applied to properties of widely differing physical characteristics. Mr. Henry takes up the subject of depreciation as applied alone to oil properties, and in doing so makes a clear distinction between amortization and the repair or renewal requirement. After carefully reading the paper the purpose of its author in suggesting a "depreciation" reserve or fund to keep the property at a constant value does not seem clear. As shown by Mr. Henry, the depreciation element as compared with the operating expense per gallon of oil is very large because of the comparatively short life of the oil properties, and it is also evident that such a "depreciation" fund would in a short time contain a very large amount of money. It seems desirable and permissible in income-tax matters to take into account the depreciation of property and to separate from the income such money as is necessary to amortize the invested capital to an extent warranted by the depreciation. However, it does not seem either necessary or desirable to create a large fund which will in time approximate the entire invested capital and which may he invested by the directors, as Mr. Henry suggests, "in the property itself or in outside securities." This method seems cumberome and liable to offer in the reinvestment of such a fund temptations to a directorate that might show more devotion to its own interests than that of the stockholders. A reserve fund is very frequently desirable in mining and oil operations, but to keep up a fund of this magnitude or to reinvest it in outside securities does not seem desirable from a stockholders' standpoint. The. money withdrawn from the receipts to be placed in the depreciation fund (not including replacements and the drilling of new wells necessary to keep up the productiveness) should he returned to the stockholders of the company, not as dividends, but as an amortization of the invested capital.

Jan 5, 1915

Frank Firmstone, Easton, Pa. (communication to tlie Secretary*) :—Mr. Dilworth's formulas hnd tables are of course correct, and the extillction will occur as calculated, provided the nioney periodically set aside for sinking-fund be really invested and the interest compounded as assumed in the calculation. Actually, in alrilost all cases, such funds are used " in the business," in which case, in addition to the periodical charges for principal of the fund, additional charges must he made at the end of each period to cover the interest and compound interest on previous charges. The periodical charge for sinking-fund thus becomes a varyillg and continually increasing one until the date of extinction. On many accounts it scems more natural and conveniellt to make the extinction by a fixed periodical charge under the legal rule for partial payments,

Jan 1, 1911