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By A. W. Sommer, H. H. Kellogg

It is shown that SO3-O2 mixtures react with sphalerite at an appreciable rate ill the temperature range of 361° to 527°C to fornz ZnSO4. The rate of reaction follows a parabolle lax. Oxygen, or O2-SO2 mixtures, have a negligible effect on sphalcrite in the same temperatuee range. PRACTICAL roasting of sphalerite is usually performed at 800°C or higher. The calcine is composed of zinc oxide unless the roaster atmosphere contains relatively large amounts of SO2 and the temperature is held to 800oC or lower, in which case zinc sul-fate may also form. Ong, Wadsworth, and assell' have made a careful kinetic study of sphalerite oxidation under these "normal conditions" and have concluded that the rate of the reaction is controlled by the decomposition of an activated complex adsorbed on the sphalerite surface. They found the rate of oxidation to be small at 700°C. Extrapolation of their data to 400°C would indicate an almost negligible rate at this temperature. In our work sphalerite was reacted with air, mixtures of SO2, O2, and N2, and mixtures of SO3, O2, and N2 in the temperature range 361o to 527OC. Negligible rates of oxidation were found, except for the gas mixtures containing SOs. With this latter gas, the oxidation of finely divided sphalerite was fairly rapid and zinc sulfate was the product. Based on the limited evidence available, the rate of sphalerite oxidation by SO3 is postulated to be controlled by gaseous diffusion through pores or cracks in the zinc-sulfate coating. This evidence for the direct reaction of sphalerite and SO, at low temperature may prove of importance to the understanding of zinc-sulfate formation in the dust-collecting equipment usually associated with zinc roasters. The roaster gas carries off fine dust, much of which may be unreacted sphalerite. The temperature in dust-collecting equipment drops from the roaster temperature (about 800°C) through the range of temperature we studied, to ambient temperature. Such dusts are known to contain far larger amounts of zinc sulfate than the primary calcine. It has been assumed in the past that this sulfate is formed by reaction of ZnO dust with SO3 (or SO, plus 0,) in the partly cooled gases. Our work shows that an alternative possibility exists—the direct reaction of SO3 with ZnS dust. EXPERIMENTAL Reaction rates for sphalerite at 350° to 600°C are relatively small so that it was necessary to use finely divided material with a relatively large surface area in order to obtain measureable amounts of reaction. In the preliminary experiments, pure mineral sphalerite, ground to pass a 325-mesh sieve, and chemically precipitated ZnS (in the form of an impalpable powder) were used. In the quantitative rate experiments the ground mineral sphalerite was processed in an Infrasizer to obtain a product with particle size between 9 and 18 µ. The analysis of this material was 66.7 pct Zn, 0.09 pct Fe, and 32.7 pct S (theoretical sphalerite is 67.1 pct Zn, 32.9 pct S). The sized powder was carefully mixed and divided into l-g samples. The apparatus used for the quantitative rate measurements is shown in Fig. 1. For the preliminary experiments the following change was made: The external catalyst furnace (B, C)* was not used. *Letters refer to Fig._______1 .___- Rather, when catalysis of the SO2 + O2 reaction was desired, the glass beads in basket M were replaced by vanadium-oxide pellets. Procedure—A l-g sample of ZnS was placed on a shallow stainless-steel tray, I, and spread evenly to a depth of about 1mm. The tray was placed in the reaction assembly and the assembly inserted in the cold furnace. The furnace tube was flushed with dry argon and then heated to the desired reaction temperature. The temperature was controlled to ±0.5oC. Gas mixtures (O2 + N2 or O2 + SO2) were prepared from tank gases by means of a mixing device identical to that employed by Darken and Gurry.2 The total flow rate of gas was 205 ml per min to point A of Fig. 1. The accuracy of the individual and

Jan 1, 1960

Have your name and address on the first page of your manuscript. Typewritten manuscript is preferred, but is not essential. If you have the manuscript typewritten, have it double spaced and written on one side of the page only; send two copies to us if convenient; only one copy of the illustrations is desired. In typewritten manuscript, formulas are better inserted by hand. Keep a copy of your manuscript in case of loss in the mail. ILLUSTRATIONS.-Photographs reproduce best when printed on glossy paper. Solio is one of the best varieties. A good print is preferable to a negative. Blueprints, drawings, or pen or pencil sketches can be used for line engravings, but care should be exercised to make them legible and clear, especially in the case of blueprints. Tracings or photographs of drawings are preferable to blueprints. Rough sketches can be used, if necessary. Photographs should be sent flat, not rolled. Do not put reference letters or other marks on photographs; if such letters or marks are necessary, fasten a piece of tracing paper to the top edge, trace a rough outline of the picture upon it and then place all letters, etc. on the tracing paper lithe exact position you wish them to appear. Restrict the number of micrographs as much as possible on account of the considerable expense involved. Standard magnifications for non-ferrous metals and alloys are recommended as follows: 10, 25, 50, 75, 100, 150, 250, 500, 750, 1000, 1500. Micrographs should be trimmed to 2 1/4 X 2 1/4 in. (six micrographs to a plate), or, if larger, up to 3 1/2 X 4 in. (two to a plate). The smaller size should be adopted if consistent with adequate representation of the subject. With each micrograph should be attached an explanatory title, together with the actual magnification, etching medium, treatment, etc., indicating what the author intends to show.

Jan 1, 1919

By R. L. Tobie

Handling and storing ore at transfer points underground are encountered frequently. An ideal solution to these troubles is probably still to be found, but at the Mather mine "B" shaft a method incorporating scraping trenches has been developed giving better service, from the standpoint of safety and simplicity, than obtained from other schemes. When shaft pockets are used for storage, the size of the ground opening required to assure capacity is often prohibitive, and shaft depth below the last level can become excessive, particularly if a crushing station is used. Also, if the material being handled contains large amounts of wet fines, it is difficult, if not impossible, to hold the material with regular chute gates. In order to remedy these problems Cleveland-Cliffs' Mather "B" has utilized three types of trenches. Types I and I1 are now in service and the third is under construction.

Jan 4, 1955

G. SHERBURNE ROGERS,* Washington, D. C. (written discussion ?).- Mr. Neal's paper on the petroleum hydrology of the Mid-Continent district is a welcome contribution on a subject concerning which none too much is known; it is, I think, the first published description of the chemical character of the oil-field waters of the great Mid-Continent area. When studying the oil-field waters of the California fields several years ago, the differences in chemical composition between waters occurring at various horizons seemed to be sufficient to enable the operators to use water analyses as a basis for determining the source of the water flooding a well; and it is gratifying to find that, Mr. Neal has arrived at a similar conclusion. As Mr. Neal points out, the Mid-Continent waters are very different in character from those of the California fields, and casual. inspection

Jan 3, 1919

By David Cole

At the time flotation appeared upon the metallurgical horizon in Arizona, the writer, under the direction of Dr. Ricketts, was engaged in remodeling and enlarging the No. 6 Concentration Plant of the Arizona Copper Co. at Morenci, and the work had been in progress nearly a year before the Inspiration experiments with flotation had disclosed the revolution in concentration that was at that time impending. The simplified flow sheet worked out for the remodeling of the Morenci plant had been based upon the removal of the freed metal in a minimum number of stages by treatment upon tables equipped with Butchart riffles, the latter being adapted to accomplish both classification of feed and removal of the metal at one operation, substantially as described in my previous paper.l The scheme of treatment for the slime was based upon the well-known fact that after copper sulphides, such as chalcocite and chalcopy-rite, etc., are reduced to a certain extremely fine state of comminution they are definitely beyond the reach of separation upon any of the concentrating devices then known. By using drag-belt classifiers (which served as conveyors as well as separators), the overflow ,would be of the usual "slimes" class. Experiment had shown that when these drag-belt overflows were properly diluted (that is, to about 5 to 7 per cent. solids in the feed under treatment) the very fine sand, and especially the very fine but still granular sulphide particles, would, if given a short distance to fall, quickly settle out in prime condition to yield an excellent recovery on vanners; a further valuable feature would be that the very fine non-separable final overflow tonnage might be discharged direct to tailing, thus conserving space requirements so as to permit within the old building, without embarrassment, the increase of capacity required. For reasons that are obvious, this kind of feed preparation for the slime could not be successfully accomplished in any form of pointed boxes or

Jan 1, 1917

By J. Campbell

The negative pressure developed within a solidifying sphere of pure iron is investigated theoretically assuming an elastic-plastic model. The maximum hydrostatic tension attainable is shown to be an order of magnitude smaller than that required for the homogeneous muclealion of pores in the liquid cove, and four orders of magnilude smaller than that predicted from) a rigid shell model. It is well-known that liquids can withstand large hydrostatic tensile stresses, or negative pressures. The various experimental investigations of the tensile strengths (often called the fracture pressures) of liquids are reviewed by Dean,1 and the theoretical attempts at estimating fracture pressures are critically assessed by wakeshima.2 Using Fisher's3 quation, the fracture pressure of pure liquid iron is about -70,000 atm, which may be too large by as much as a factor of 4, but is certainly correct to within an order of magnitude.' In view of the great importance of the problem of the nucleation of shrinkage cavities in castings it is of interest to determine exactly what tensile stresses can exist in the residual liquid in a solidifying casting; it has often been assumed that, because of the very low strengths of solid metals near their melting points, no interior stresses are developed at all. Nussey4 has determined theoretically the pressure in the liquid core of a solidifying metal sphere assuming that the solidified shell does not deform (i .e., is perfectly rigid), so that because of the contraction accompanying solidification (a) (about 3 pct for most metals) the progressive deposition of solid onto the inner surface of the shell causes the remaining liquid to be expanded to make up this difference in volume. This leads to a relation between the pressure P in the liquid, the initial pressure, PO, the bulk modulus of the liquid, K, and the inner and outer radii of the solid shell, o and b, respectively:

Jan 1, 1968

By Ursula E. Wolff

Il.lechanica1 twins have been observed in brigsten single crystals of a variety of axial orientations defornzed at room temperature in tension or bending. The twins formed near the final fracture and were up to 3 p thick. The twinning plane was always of the type (113). Twinning at room ternperature occurred only after considerable prior slip. Twins usually preceded fracture and nucleated cracks. The crack surfaces often alternated between a (001) plane and the twin interfaces. Secondary twins could also nucleate from cracks. In the absence of twinning tensile samples failed by shear; twinned samples failed by cleavage. On the assumption that observed sudden load drops in the stress-strain curves are associated with twinning, a critical resolved stress for twinning of 60, 000 to 65, 000 psi was calculated. MeCHANICAL twinning has been observed in iron and iron alloys at low temperature by a number of investigators.'-7 Similarly, for high-purity tungsten, twinning has been reported for deformation temperatures below 211°K.8-10 In W-Re and Mo-Re alloys, 20 pct Re was determined as the lower limit for twin formation at room temperature." Since the twins are generally very narrow, they are usually identified only by etching techniques. The expected (112) habit plane has always been confirmed by angular analysis of the surface traces. Recently, however, a complete identification by X-ray analysis has been performed on twins in a Mo-35 pct Re alloy.12 During an investigation of the deformation charac- teristics of tungsten single crystals, twins were revealed in tensile and bend samples deformed at room temperature. This paper deals with the conditions for such twinning and the relation of twinning to fracture. EXPERIMENTAL PROCEDURE Tungsten single crystals, 1/8 in. in diam, of a variety of axial orientations were grown from un-doped material by four-pass electron-beam zone melting. A representative analysis is given in the following table: From these crqstals, tensile samples with 1 in. gage lengths were made by surface grinding, leaving shoulders for gripping. The diameter after grinding was 0.082 in. The distorted surface layer was then removed by ele1:trolytic polishing which reduced the diameter of the gage length to 0.080 in. Tensile tests were carried out at room temperature in an Instron machine under two different sets of conditions: a) Rigid mounting; strain rate 0.02 in. per in. per min. b) Gimbal mounting; strain rate 0.002 in. per in. per min up to a total strain of approximately 0.2 pct, then 0.01 in. per in. per min to fracture. Stress axis and growth direction coincided in all samples and are subsequently called orientation.

Jan 1, 1962

R. B. T. KILIANI, Denver, Colo. (written discussion *).-Mr. Len-nox's paper is decidedly interesting in that he shows that a field exists for the Chilean mill, in which its efficiency compares favorably with that of more modern grinding devices. The figures he has given clearly indi-cate that a coarse feed is conducive to higher efficiency than the fine feeds which the Chilean mill has usually been called upon to grind. The fact is also apparently indicated that operating the Chilean mill in closed circuit with a mechanical classifier results in still higher efficiency, and that in such cases the percentage of returns should be kept below 100 per cent. to obtain best results. It would be interesting to see the results of further tests with what Mr. Lennox calls "Mixed Feed," since the data given in Table 4 seems to' point to the fact that a mixed feed,

Jan 12, 1919

By R. J. Shaffer

Hydraulic fracturing in rock masses involves complex and coupled processes of fractures propagating in discontinuous media and of fluid flow in discrete channels. The Unconventional Gas Program at LLNL is actively developing numerical models to gain insight in the physics of these coupled processes. This paper describes the current status of the FEFFLAP code, which models fluid-driven discrete fracture propagation in jointed media. We also discuss the results of a preliminary series of physical tests in which hydrofractures were driven across slanted interfaces between dissimilar materials, in blocks loaded in biaxial compression.

Jan 1, 1984

By A. G. Worthing

Black: Bodies.-In the ordinary conception, a black object is an opaque object that reflects but little of the light that is incident on it. This means naturally that such an object is a good absorber of luminous radiation. The black body; which is so closely connected with high-temperature measurements, represents the limit in blackness of all black objects. It is a body that not only absorbs all visible radiations but also all other radiations in the infra-red and the ultra-violet regions of the spectrum which are incident on it. No substance is known that is completely black; platinum black, one of the nearest if not the nearest representative of the ideal, reflects 1 per cent. or so of ordinary visible radiation. The closest approach to the ideal is a small opening in the wall of a relatively large opaque cavity. Any radiation incident on this black body will be almost completely absorbed if the relative dimensions are properly chosen no matter what the material may be. The great difference between the blackness of such a cavity and of lampblack, for instance, will be apparent to one who makes the simple test. Non-black Bodies.-The field of non-black bodies covers all real bodies. Their characteristics are extremely varied. So far as absorption of radiation-is concerned, these bodies range practically from the almost completely black, platinum-black, and lampblack, which absorb all but a fractional part of 1 per cent. or so of the incident radiation, by an infinite variety of steps to freshly polished silver, which ordinarily absorbs only a few per cent. The exact percentage absorbed depends not only on the nature of the incident radiation, but also on the temperature of the body, the condition of its surface, the angle of incidence, the nature of the surrounding medium, and on certain other less important conditions. As consequences of these varied characteristics, we have not only the differences of color of ordinary objects, but also the changes of color that any one object undergoes on heating or when lighted front various directions. This complexity of the phenomena, in a way, is responsible for the meagerness of knowledge, regarding materials at elevated temperatures. Measurement of High Temperatures.-Excepting in cases where the thermocouple or the gas thermometer are applicable, in which case the temperatures obtained are true temperatures regardless of-the material" studied, high, temperatures are almost always, if not always, determined from measurements of radiation. In fact, determinations of temperature from this latter point of view are often so much more convenient than the thermocouple and especially the gas-thermometer determinations that, in the region where all of these types of measurements may be made, the radiation measurements are often preferred. This is true even though the temperatures usually thus directly determined are not the actual temperatures, a consequence of the sources of the radiation being non-black bodies; in other words, a consequence of being concerned with iron, or glass, or tungsten instead of small openings leading to relatively large-cavities uniformly heated. Coordination of Experimental Results.-In order that data on iron, glass, tungsten, or other non-black bodies obtained in one laboratory, may be, correlated with similar data obtained elsewhere, temperatures must be expressed on a common scale. The true temperature scale is the natural scale for this purpose it is ordinarily the scale to which all other temperatures can be most directly reduced. When the measurements depend on the radiation, a knowledge of emissive powers repre-

Jan 9, 1919

By H. Landssberg

Subsidence caused by mining operations has been a matter of interest for the mining engineer for just 111 years, since the Belgian committee for study of subsidence in the city of Liege submitted its first report in 1825. This interest is fairly expressed in the enormous amount of literature that has since appeared on this subject. A bibliography, probably far from being complete, which preceded this study as a preliminary survey, comprises more than 800 titles. In spite of this fact the problem remains today as acute as it has ever been. The questions of as good a recovery as possible of the national resources, the safety of the operations, and the protection of private and public property are the important angles from which to look at the problem. The Problem To systematize an investigation regarding the effects of mine excavations two different aspects have to be dealt with: (1) the subsidence of the immediate roof above the workings, affecting the safety of the workers and the progress and efficiency of the operations; (2) the subsidence of the surface, which is also, from the point of time, the second event. The immense importance of surface subsidence as regards the impairment of surface structures of every kind in a mining area is self-evident. Both effects result from reactions of the strata overlying the excavations and they depend mainly on the extent of the excavations and the structure and geological condition of the strata. It has been stressed repeatedly, in this country principally by G. S. Ricel,† that for the understanding of the phenomenon of subsidence accurate surveys are the most urgent necessity. In the past, however, at least in the normal course of mining operations, these surveys have been very crude. The control of the roof in the mine is left to the observation of the behavior of the timber, warning cracks and sounds in roof and walls and to the general judgment and experience of the worker and his supervisors. In any given case this may or may not be sufficient to prevent fatalities but certainly it does not give any accurate information as to what is happening in roof and strata. On the surface, principally in endangered areas, surveys have been conducted more frequently, but also in this case usually weeks or even

Jan 1, 1936

By H. Landssberg

Subsidence caused by mining operations has been a matter of interest for the mining engineer for just 111 years, since the Belgian committee for study of subsidence in the city of Liege submitted its first report in 1825. This interest is fairly expressed in the enormous amount of literature that has since appeared on this subject. A bibliography, probably far from being complete, which preceded this study as a preliminary survey, comprises more than 800 titles. In spite of this fact the problem remains today as acute as it has ever been. The questions of as good a recovery as possible of the national resources, the safety of the operations, and the protection of private and public property are the important angles from which to look at the problem. The Problem To systematize an investigation regarding the effects of mine excavations two different aspects have to be dealt with: (1) the subsidence of the immediate roof above the workings, affecting the safety of the workers and the progress and efficiency of the operations; (2) the subsidence of the surface, which is also, from the point of time, the second event. The immense importance of surface subsidence as regards the impairment of surface structures of every kind in a mining area is self-evident. Both effects result from reactions of the strata overlying the excavations and they depend mainly on the extent of the excavations and the structure and geological condition of the strata. It has been stressed repeatedly, in this country principally by G. S. Ricel,† that for the understanding of the phenomenon of subsidence accurate surveys are the most urgent necessity. In the past, however, at least in the normal course of mining operations, these surveys have been very crude. The control of the roof in the mine is left to the observation of the behavior of the timber, warning cracks and sounds in roof and walls and to the general judgment and experience of the worker and his supervisors. In any given case this may or may not be sufficient to prevent fatalities but certainly it does not give any accurate information as to what is happening in roof and strata. On the surface, principally in endangered areas, surveys have been conducted more frequently, but also in this case usually weeks or even

Jan 1, 1936

By E. R. Hoskins

Results of a primary stress measurement investigation conducted on the 1100 copper ore body of the Mt. Isa mine, Mt. Isa, Queens., Australia, are presented in this chapter. The investigation started in September 1965, after discussion with the engineering staff at Mt. Isa, and consisted of both underground or in-situ tests at Mt. Isa and laboratory tests on Mt. Isa rocks and stress measurement techniques at the Australian National University in Canberra. Underground stress measurements were made in and adjacent to the 1100 copper ore body. The primary stress measurement site was in J 32 west crosscut on 14 Level. Approximate coordinates on the mine grid are 3000 north, 1650 east. The vertical depth below ground surface at this point is approximately 2180 ft. Some preliminary measurements were made in M 30 west crosscut on 13 Level, coordinates 3000 north, 2000 east, depth beneath the surface approximately 1990 ft. Additional flatjacks were installed on 11 Level in L 30 west crosscut, coordinates 3000 north, 2200 east, and depth beneath the surface approximately 1580 ft. All of the sites were in rock that from a mining engineering viewpoint must be considered extremely sound. The 13 and 14 Level crosscuts were approximately 14 ft on a side and nearly square and the 11 Level crosscut was approximately 10 ft on a side. All of the crosscuts had been standing open for several years and no artificial support of any type was necessary. Extraction openings hundreds of feet on a side have been made in this mine in similar rock and these have remained open also without additional support (see Davies 1 for a recent summary of mining techniques and conditions). The geology of the Mt. Isa mine has been most recently described by Bennett.2 Briefly, Mt. Isa is a silver-lead-zinc and copper mine in a series of Precambrian siltstones, shales, and bedded carbonates that strike north-

Jan 1, 1972

By B. D. Crawford, S. A. Falconer

ONE of the outstanding achievements in connection with this country's war efforts has been the ability of our mining industry to supply from domestic sources many of the minerals of strategic importance that formerly were obtained principally from abroad. In order to meet the war-born demands for these scarce minerals, it has frequently been necessary to develop special methods for treating ores and waste products hitherto considered too low-grade to be workable; and to improve the efficiency of older beneficiation processes. Important in this respect have been the recent technological advances in the field of froth flotation of nonsulphide minerals. Because of the refractory nature of many of these domestic ores, and, in many cases, the limited available technical data regarding their treatment, much research work has been necessary. The following examples describe the procedures and reagents used, and the results obtained, in certain laboratory flotation investigations conducted by American Cyanamid Company's engineers at the Cyanamid Ore Dressing Laboratory on ores containing such minerals as scheelite, manganese oxides and carbonate, ilmenite, brookite, kyanite, garnet, spodumene, mica, feldspar, celestite, fluorite, chromite, corundum, and cassiterite. In presenting these data, we wish to point out that many of the minerals listed have previously been tested, and their amenability to flotation reported, by other investigators-notably those of the United States Bureau of Mines. In some instances the procedures and reagents used in the treatment of some of the following described ores follow rather well-established lines, and with one or two exceptions, the reagents used were well known. However, many of the ores tested did not respond well to simple conventional procedures and it was necessary to adopt special methods of conditioning and desliming, reversal of the usual order of floatability of some of the minerals, multiple cleaning, etc., in order to secure separations. Except where otherwise noted, all numbered and trade-marked reagents mentioned in this paper are marketed by the American Cyanamid Co. or the American Cyanamid and Chemical Corporation. TUNGSTEN ORES Tungsten minerals, vitally important in the war industries of the United States, rank high in the list of those we formerly had to import in order to supply our needs. Most of our domestic ores of tungsten contain scheelite as the valuable mineral. Today there are in the neighborhood of twelve tungsten operations in this country where flotation is used as the main or accessory form of benefication. It has, of course, been known for some time that scheelite and other tungsten minerals respond to treatment by flotation.

Jan 1, 1944

By W. W. Smeltzer

The linear formation rates of wustite films have been determined over the temperature range 590° to 1030°C using a vacuum microbalance technique. These rates are dependent directly on the partial pressure of carbon dioxide, Activation energies for film and scale formation in carbon dioxide and oxygen atmospheres are equivalent to either the dissociation energies of carbon dioxide and oxygen, or the activation energy for the diffusion of cation vacancies in wustite. Of the metals, iron is the most widely used basic constituent of durable alloys despite its intrinsic property of converting at a relatively rapid rate to the oxides from which it is derived. This property has accounted partially for many investigations on the oxidation of iron at low and high temperatures. Interpretation of the results have been complicated by formation of multilayers containing the various oxide phases. To aid in elucidation of the oxidation kinetics, measurements have been carried out in this investigation on the growth of the wustite surface layer. There are several studies directly related to the objective of this investigation. The growth of multilayer scales has been demonstrated to be diffusion controlled in oxygen at atmospheric pressure over the temperature range 450" to 1200°C by Davies, Simnad, and Birchenall.' To gain an insight into the diffusion mechanism, Himmel, Mehl, and ~irchenall' determined the self-diffusion coefficients of iron in wustite, magnetite, and hematite. These results were used to evaluate the oxidation rates of iron and its oxides, taking as a basis the theoretical parabolic rate equation developed by Wagner., The evaluations were compared to experimental data and were shown to provide essential confirmation of this theory. Fischbeck, Neundeubel, and salzer4 have demonstrated that the oxidation of iron in carbon dioxide and other atmospheres at high temperature obeys a linear relationship. Because the Arrhenius temperature coefficients of the reaction rate constants changed at the A, point they concluded that the passage of iron into the oxide controlled the reaction. This viewpoint has been accepted by Benard and ~albot' to explain the occurrence of linear rates in oxygen before the onset of diffusion-controlled parabolic oxidation. This basic premise of a rate-controlling reaction at the iron/oxide interface has been questioned recently by Hauffe and Pfeiffer.' Since the formation of wustite may follow a linear or parabolic relationship depending on the pressure of the gaseous re-actant, they propose that linear oxidation is determined by a chemisorption reaction while parabolic oxidation is controlled by diffusion. As confirmation of this viewpoint, Hauffe and pfeiffer6 and Pfeiffer and ~aubmeyer' have established that the linear scaling constants of wustite formation at 1000°C in carbon-dioxide or low-pressure oxygen atmospheres

Jan 1, 1961

By Walter Kauzmann

EyRing'S general theory of shear rates as a function of the properties of molecular units of flow is outlined and applied to the creep of metals. This theory regards the unit molecular processes involved in the flow of matter as typical chemical reactions requiring an energy of activation in order to proceed. The externally applied stresses are assumed to influence the rate of flow solely by lowering the activation energy for flow in one direction and raising that for flow in the other, owing to the work that is done by or against the external forces in going from the normal to the activated state. The rates of flow in the two directions are then no longer equal arid there is a net, macroscopically observable flow in one direction. This is understood to be the physical basis for the well-known exponential dependence of the creep rate on the stress. The amount by which the activation energy is raised and lowered by a given external stress is directly related to the molecular dimensions of the unit of flow, so that some insight into these call be found from the behavior of the strain rate with changing stress. When Eyring's equation is applied to the flow of ordinary liquids, such as water or benzene, it has been found from the values of the constants required to fit the observed data that the unit molecular process here involves the passage of single molecules by one another. In metallic creep, on the other hand, the unit molecular process is shown probably to involve the shear of rather large blocks of material (100 to 1000 or more atoms on a side). This agrees with present ideas of crystal flow by means of dislocations such as have been presented by Taylor, Oroaan, and Polanyi, as opposed to flow by a mechanism related to that taking place in atomic diffusion. The dimensions of the dislocations are found to depend markedly on the temperature. The questions of why some metals are so much softer than others, the effects of impurities on hardness, the softness of single crystals, and the role of self-diffusion in creep are considered in the light of the theory and it is shown how answers to these questions (and others similar) might be obtained by use of the theory.

Jan 1, 1941

By Walter Kauzmann

EyRing'S general theory of shear rates as a function of the properties of molecular units of flow is outlined and applied to the creep of metals. This theory regards the unit molecular processes involved in the flow of matter as typical chemical reactions requiring an energy of activation in order to proceed. The externally applied stresses are assumed to influence the rate of flow solely by lowering the activation energy for flow in one direction and raising that for flow in the other, owing to the work that is done by or against the external forces in going from the normal to the activated state. The rates of flow in the two directions are then no longer equal arid there is a net, macroscopically observable flow in one direction. This is understood to be the physical basis for the well-known exponential dependence of the creep rate on the stress. The amount by which the activation energy is raised and lowered by a given external stress is directly related to the molecular dimensions of the unit of flow, so that some insight into these call be found from the behavior of the strain rate with changing stress. When Eyring's equation is applied to the flow of ordinary liquids, such as water or benzene, it has been found from the values of the constants required to fit the observed data that the unit molecular process here involves the passage of single molecules by one another. In metallic creep, on the other hand, the unit molecular process is shown probably to involve the shear of rather large blocks of material (100 to 1000 or more atoms on a side). This agrees with present ideas of crystal flow by means of dislocations such as have been presented by Taylor, Oroaan, and Polanyi, as opposed to flow by a mechanism related to that taking place in atomic diffusion. The dimensions of the dislocations are found to depend markedly on the temperature. The questions of why some metals are so much softer than others, the effects of impurities on hardness, the softness of single crystals, and the role of self-diffusion in creep are considered in the light of the theory and it is shown how answers to these questions (and others similar) might be obtained by use of the theory.

Jan 1, 1941

By C. F. Rust

Experimental evidence is presented showing that reproducible formation resistivity factor measurements and resistivity index determinations on reservoir core samples map be made utilizing either the two- or four-electrode methods. Equipment is described which permits the application of either technique to the core specimen without loss of time and with a minimum amount of effort. Since electrical resistivity measurements on reservoir rocks are important not only in electric log interpretations, but also in the study of fundamental rock parameters, it was considered desirable to compare the applicability of both techniques of resistivity measurement. INTRODUCTION The techniques employed in the measurement of electrical resistivity on reservoir rocks, as practiced in the petroleum industry, may be reduced to two fundamental methods: one utilizing two electrodes only, usually referred to as the two-electrode method; the other using two additional electrodes and commonly known as the four-electrode method. In the former, the core sample whose resistivity is to be measured is mounted between two electrodes, usually metal discs, which serve to pass a current of known magnitude through the saniple. The potential drop across the sample, measured between these same two electrodes, and the core dimensions furnish the necessary data to compute he resistivity of the sample. In the four-electrode technique the end plates, again usually ol metal, still serve as current electrodes. Additional probes or electrodes dispersed along the sample are utilized to measure the potential drop. Both methods are used in practice1,2 and it is the purpose of this paper to compare the two techniques as applied to the determination of formation reiistivity factors and the resistivity index exponent n, in Archie's empirical equation I = p/po = Sw 11. To evaluate the two techniques it is desirable to point out the experimental precautions which must be taken to insure reliable results. It is evident from the electrode arrangements of the two- and the four-electrode methods that, for a given sample, the volume of sample included by the four-electrode method is less than the volume included by the two-electrode method. One of the prime difficulties associated with the two-electrode method is the possible occurrence of an abnormally high resistance between the electrodes and the brine-saturated sample, which results in erroneous resistivity values for the core sample itself. Attempts to alleviate this difficulty meet varying degrees of success. Methods used in the past employ such absorbent materials as brine-saturated Kleenex: chamois, or felt. A technique described by Morgan, Wyllie, and Fulton,1 appears to be more satisfactory. Their method consists of spraying or painting the end areas of a core sample with conductive silver paint. This technique reduces contact resistances between the porous medium and the electrodes to a value which is generally negligible as compared to the resistance of the sample itself. In the four-electrode method these requirements are not as stringent since separate probes are used to measure the potential difference acrozs a portion of the sample. In this case, contact resistance occurring at the current electrode; are of no consequence. and those appearing at the potential

Jan 1, 1952

By Daniel R. Hull

IN 1026 Genders' reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan,3 and by Phillips and Brick,2 so that no resume is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. VAPOR SEGREGATION There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table I, which represents a [ ] cylindrical billet 7 in. in diameter by 5; in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. The lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps up a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By Albert Sauveur

My first paper dealing with the theories of the hardening of steel by rapid cooling was published in the Transactions of this Institute in 1896— 30 years ago-under the title "The Microstructure of Steel and the Current Theories of Hardening," hence, also, the title of the present paper. It was extensively discussed and was, I believe, one of the starting points of many subsequent papers and discussions of the same subject, dis-cusssions which at times became almost violent and which led to the formation of different schools such as the "Carbonists" and the "Allo-tropists." Some of the older members of the Institute, who took part in the debate or who were interested observers, will, I am sure, have kept a vivid remembrance of it. The controversy gradually quieted down, apparently for lack of ammunition, without any side acknowledging defeat. Recently, however, interest in it ha been revived through the claims of some that these vexed questions had at last been solved. In an effort to ascertain if possible the prevailing view of those best qualified to express an opinion a questionnaire was submitted to the following gentlemen: J. 0. Arnold Sir Robert Hadfield Edgar C. Bain W. H. Hatfield Carl Benedicks Samuel L. Hoyt N. Belaiew Kotaro Honda H. M. Boylston Zay Jeffries Harry Brearley H. Le Chatelier G. K. Burgess H. H. Lester William Campbell Francis F. Lucas H. C. H. Carpenter John A. Mathews Pierre Chevenard A. McCance P. Dejean Albert Portevin C. A. Edwards Walter Rosenhain F. Giolliti Bradley Stoughton G. Grenet F. C. Thompson Leon Guillet

Jan 1, 1926