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By M. L. Samuels

In a recent paper the authors1 discussed the reactions to tempering of hypereutectoid steels quenched from 1000' C., as revealed by studies on changes in hardness, electrical resistivity, coercive force and metallo-graphic charaeteristics. The data, which related specifically to tempering temperatures of 550°, 650" and 710" C., for varying periods up to 125 hr., permitted the following important conclusions: 1. The rate of softening of the steels at the temperatures examined differed markedly although the steels were of "similar" general chemical composition. 2. The temperature of maximum softening spread over a range from about 650" C, to the eutectoid inversion. 3. The divergence in behavior was ascribed, at least in part, to a profound difference in tendency to graphitization on annealing at sub-eutectoid temperatures. 4. The mode of spheroidization of the cementite, as revealed by metallographic studies, also varied considerably in the different steels. The purpose of the present investigation is to pursue further the study of the difference in behavior of the steels on tempering over a wider range of temperature. To this end the following features have received particular attention: 1. Comparison of temperatures of maximum softening of the various steels when the quenched samples were tempered for 5 hi. and for 75 hr. followed by furnace cooling and by quenching in water. 2. Deterrnirlation of the effect of quenching temperature, prior to tempering, on the rate of softening. Quenching temperatures of 1000" and 850" C. were used in the investigations. 3. Examination of the microstructures obtained with the various heat-treatments employed.

Jan 1, 1938

By B. S. Norris, Charles R. Austin

IN a recent paper the authors1 discussed the reactions to tempering of hypereutectoid steels quenched from 1000° C., as revealed by studies on changes in hardness, electrical resistivity, coercive force and metallographic characteristics. The data, which related specifically to tempering temperatures of 550°, 650° and 710° C., for varying periods up to 125 hr., permitted the following important conclusions: 1. The rate of softening of the steels at the temperatures examined differed markedly although the steels were of "similar" general chemical composition. 2. The temperature of maximum softening spread over a range from about 650° C. to the eutectoid inversion. 3. The divergence in behavior was ascribed, at least in part, to a profound difference in tendency to graphitization on annealing at subeutectoid temperatures. 4. The node of spheroidization of the cementite, as revealed by metallographic studies, also varied considerably in the different steels. The purpose of the present investigation is to pursue further the study of the difference in behavior of the steels on tempering over a wider range of temperature. To this end the following features have received particular attention: 1. Comparison of temperatures of maximum softening of the various steels when the quenched samples were tempered for 5 hr. and for 75 hr. followed by furnace cooling and by quenching in water. 2. Determination of the effect of quenching temperature, prior to tempering, on the rate of softening. Quenching temperatures of 1000° and 850° C. were used in the investigations. 3. Examination of the microstructures obtained with the various heat-treatments employed.

Jan 1, 1938

By A. B. Kinzel

PRECISE knowledge regarding the effect of heat treatment on the properties of steel has made possible the detailed specifications and instructions covering optimum heat-treating temperatures and practices that are in current use. A distinct contrast is presented by the metal-lurgical treatment of steel adjacent to a fusion weld, as such steel is subjected to each, temperature from room temperature to fusion tempera-ture, and cooled at a rate that is not generally controllable but is pre-determined by the nature of the assembly to be welded, the kind of welding used, and the surrounding conditions. This is true regardless of the type of fusion welding: oxyacetylene, electric arc, thermit or flash resistance. Therefore it seemed desirable to investigate the effect of this metallurgical treatment on the characteristics of carbon steels commonly used for welding, by a detailed study of metal subjected to each temperature range; i.e., each heat-affected zone. Oxyacetylene welding was chosen for the investigation because of the experimental facility of accurately segregating and studying each tem-perature zone. The nature of the zones produced by other types of welding is the same. The difference is primarily a matter of dimensions of each of the temperature zones involved. The advantages and dis-advantages of the extent of the zone are of prime moment, and are dis-cussed after the presentation of the detailed zone study. No mention is made of the fused metal proper, as this has been the subject of much published research and the nature of the solidified metal is fairly well known.

Jan 1, 1935

By Charles Austin

IN a recent paper the authors1 discussed the reactions to tempering of hypereutectoid steels quenched from 1000° C., as revealed by studies on changes in hardness, electrical resistivity, coercive force and metallo-graphic characteristics. The data, which related specifically to temper-ing temperatures of 550°, 650° and 710° C., for varying periods up to 125 hr., permitted the following important conclusions: 1. The rate of softening of the steels at the temperatures examined differed markedly although the steels were of "similar" general chemi-cal composition. 2. The temperature of maximum softening spread over a range from about 650° C. to the eutectoid inversion. 3. The divergence in behavior was ascribed, at least in part, to a profound difference in tendency to graphitization on annealing at sub-eutectoid temperatures. 4. The mode of spheroidization of the cementite, as revealed by metallographic studies, also varied considerably in the different steels. The purpose of the present investigation is to pursue further the study of the difference in behavior of the steels on tempering over a wider range of temperature. To this end the following features have received particular attention: 1. Comparison of temperatures of maximum softening of the various steels when the quenched samples were tempered for 5 hr. and for 75 hr. followed by furnace cooling and by quenching in water. 2. Determination of the effect of quenching temperature, prior to tempering, on the rate of softening. Quenching temperatures of 1000° and 850° C. were used in the investigations. 3. Examination of the microstructures obtained with the various heat-treatments employed.

Jan 1, 1938

By Yehia M. Eyssa

A "straight wire" flow through magnetic ore separator has been designed, built and successfully used to separate magnetite from typical slurries. The purpose of these experiments was to simulate the high field profile of a "straight wire" superconducting magnetic separator which would be capable of separating weakly magnetic hematite ore from typical slurries. Magnetite was used as the test mineral because it experinces the same magnetic forces at low field as does hematite at high field. The present separator concept is based on the fact that there is a particle concentration profile due to the gravity field for low velocity turbulent flow. When a magnetic field force of -g is applied the concentration profile of the magnetic particles will be reversed leaving the nonmagnetic particles flowing alone at the bottom of the channel. By means of a divider at the end of the channel the concentrate is separated from the tailings. It is shown that the time needed to deflect hematite particles in a narrow cylindrical channel concentric with the superconducting wire is small enough so that high throughputs in the turbulent flow region are possible. In the case of a high field superconducting separator the centrifugal force could replace gravity by rotating the flow around the straight wire conductor.

Jan 1, 1974

By AIME AIME

THE Western States Joint Convention opened at Denver on Sept. 20, with about 400 registered the first day. Monday was devoted to the American Mining Congress, and the afternoon session was taken up with a discussion of the public land laws of the United States. Hubert Work, Secretary of Interior, and William Spry, Commissioner of the General Land Office, presented a comprehensive review of the origin and operation of the laws and argued against any general change in the system. Charles E. Winter, Congressman from Wyoming, marshalled the arguments in favor of turning over the public lands to the states within which they lie, and George H. Dern, Governor of Utah, presented a well-reasoned argument in favor of allowing the school sections to pass to the states regardless of their mineral or non-mineral character. The debate made it clear that in the West especially, there is strong feeling against any further development of the policy of reserving and leasing the public lands. Tuesday forenoon was devoted to the Silver Producers Association, F. H. Brownell and Charles A. Thomas being the principal speakers, and in the after- noon the American Association of Petroleum Geologists met with Alex. W. McCoy presiding, and Glenn C. Clark, J. V. Howell, and J. W. Beede presenting papers.

Jan 1, 1926

By Ljudmil S. Grigorov, Eric Forssberg, Hanumantha Rao Kota, Robert J. Pugh, Lidia B. Alexandrova

"We have used the microscopic thin balance developed by Scheludko at al. (1970) technique to study the stability and interactions within the thin film between the silica surface and air bubble with (i) a long chain C10 amine and (ii) a cationic/anionic surfactant systems consisting of mixtures of a long straight C10 chain amine with long straight chain C8, C10 and C12 sulfonates. It was found that the mixed surfactants caused lower contact angles, lower rates of the thin aqueous film rupture and longer film lifetime, compared to the pure amine system.This behavior was explained by the initial strong adsorption of positively charged interfacial complexes from the mixed surfactant system at the air/solution interface followed by adsorption at the silica interface. It was also shown that the chain length compatibility between the anionic and cationic surfactants controls the strength of the interfacial complex, determining an inhibition in the thin film rupture and dewetting of the film. The rupture mechanism was explained by an earlier established heterocoagulation mechanism between the positively charged air/solution interface and the solution/silica interface which remained negatively charged. The formation of the interfacial complex at the air/solution interface was confirmed by using surface tension data."

Jan 1, 2003

By William E. Dennis

"INTRODUCTION The San Antonio Canyon prospect was examined by engineers 3/ of the Bureau of Mines in March 1943 and again in October 1944. In July 1944, the United States Geological Survey mapped the prospect and submitted a report 4/ recommending core drilling by the Bureau of Mines. The drilling project, which was supervised by the author, was started on January 10 and completed on May 10, 1946.ACKNOWLEDGMENTSIn its program of investigation of mineral deposits, the Bureau of Mines has as its primary objective the more effective utilization of our mineral resources to the end that they make the greatest possible contribution to national security and economy. It is the policy of the Bureau to publish the facts developed by each project as soon as practicable after its conclusion. The Mining Branch, Lowell B. Moon, chief, conducts preliminary examinations, performs the actual investigative work, and prepares the final report. The Metallurgical Branch, O. C. Ralston, chief, analyzes samples and performs beneficiation tests. Acknowledgment is made to W. D. McMillan, engineer in charge of the Austin field office, and to J. H. Hedges, chief of the Tucson Division, Mining Branch, for general direction and advice. The samples were analysed in the laboratory of the Metallurgical Branch at Rolla, Mo., C. Travis Anderson, chief."

May 1, 1947

By N. S. Tanious

This paper summarizes the results of an investigation into possibly the largest coal pillar failure in the USA. The newly opened drift mine is located in Southeastern Kentucky and worked an 11 feet thick coal seam, all other mines in the District worked seams 4-5 feet thick. The initial mine development consisted of 14 main entries (Fig. 1) which were driven in two sets of 7, under increasing depth of overburden. As the left seven entries came under deeper overburden the pillar ribs began sloughing which caused many of the concrete-block ventilation stoppings to crack. The mine management stopped the advance in the left seven and continued with the right seven entries. During the spring of the following year development resumed in the left seven, rib sloughage occurred again and this time severely cracked many stoppings and many were totally disintegrated from the excessive deformation. Within few weeks the sloughage was so heavy that many of these entries behind the active face were filled with piles of sloughed coal slabs. When the face reached a depth approximately 1150 feet, the sloughage became a slow, massive squeeze. The entry convergence (closure) reduced their height from 11 to 7-8 feet and the squeeze spread back to shallower depth covering an area roughly 300 pillars.

Jan 1, 1989

By T. B. Counselman

C. G. McLachlan—In the foregoing paper the author has presented a very neat method for calculating the solution recovery for a countercurrent flowsheet. He has, however, based his calculations, as he states, on the assumption that "the concentration of dissolved value must be exactly the same in the overflow and underflow of any thickener." This assumption, which is usually made regardless of the type of calculation used, is "not strictly correct because diffusion of the dissolved gold in the solution associated with the solids as it progresses through the countercurrent system is far from being instantaneous, with the result that on a ton for ton basis, the assay of the solution in the thickener underflow is higher than in the corresponding thickener overflow. An agitator introduced into the flowsheet between thickeners will reduce, but not entirely eliminate, this difference. In practice we have found that the best way to take care of this condition— in addition to the use of one or more intermediate agitators—is to circulate 20 pct or 25 pct more solution than called for by the cheoretical calculation. This presents no difficulty provided that adequate thickener capacity is provided in the original design of the countercurrent circuit.

Jan 1, 1951

By T. B. Counselman

C. G. McLachlan—In the foregoing paper the author has presented a very neat method for calculating the solution recovery for a countercurrent flowsheet. He has, however, based his calculations, as he states, on the assumption that "the concentration of dissolved value must be exactly the same in the overflow and underflow of any thickener." This assumption, which is usually made regardless of the type of calculation used, is "not strictly correct because diffusion of the dissolved gold in the solution associated with the solids as it progresses through the countercurrent system is far from being instantaneous, with the result that on a ton for ton basis, the assay of the solution in the thickener underflow is higher than in the corresponding thickener overflow. An agitator introduced into the flowsheet between thickeners will reduce, but not entirely eliminate, this difference. In practice we have found that the best way to take care of this condition— in addition to the use of one or more intermediate agitators—is to circulate 20 pct or 25 pct more solution than called for by the cheoretical calculation. This presents no difficulty provided that adequate thickener capacity is provided in the original design of the countercurrent circuit.

Jan 1, 1951

By John B. Goodman

This report presents a study of a modification of the precision laboratory carbonization-assay apparatus that renders the unit capable of performance at low-, medium-, and high-temperature assay levels and permits, under controlled conditions, evaluation of the relationship between carbonization temperature and the yield of pyrolysis products. Second, the interest and value derived from the temperature study data directly apply to the particular semiplant carbonization processes and techniques currently being investigated in this laboratory. Data obtained with the assay apparatus enables the fuel technologist to predict the probable yields of carbonization products from pilot-plant operations under various carbonizing conditions. Data obtained with the assay apparatus has been used to predict the product yields of industrial carbonization plants at Kemmerer, Wyo., and Rockdale, Tex. The assay provides a useful tool in detecting, from the carbonized plant product, the degree of effectiveness of pilot-plant operation. Third, the residual volatile matter in some industrial carbons has broad significance. Evaluation of the volatile material remaining with or in the carbon may be assessed through the high-temperature-assay technique. The low-temperature carbonization assay devised by the writers has proved to be a versatile tool in predicting the probable product yields from pilot-scale carbonization processes. The apparatus described in previous publications has been modified to extend the range of testing above 500° C. without impairing the accuracy and reproducibility obtained in the low-temperature range. Results presented here include product yields from a typical Texas lignite and Wyoming subbituminous-B-rank coal over the temperature range 150° to 1,000° C.

Jan 1, 1958

By James Douglas

PROBABLY no well-informed engineer would ques¬tion the accuracy of the statement that the piece of equipment that comes nearest to being in universal use in modern hydrometallurgical and ore-dressing plants is the Dorr continuous thickener. The function of the device is to separate a thin mixture of liquid and solid particles into a thick pulp and a clear liquor. Another machine in wide use is the Dorr classifier, the purpose of which is to separate the coarse and fine particles in a pulp containing solids of various sizes. It is in recognition of the invention of these two devices and the vast amount of technical work in the successful application of them in the beneficiation of ores that the James Douglas Medal for 1930 has been awarded to John Van Nostrand Dorr. To gage the importance of the development of the thickener, particularly, it is only necessary to imagine the loss of time, capacity, and metallurgical efficiency that would result if all the Dorr tanks in the world were put out of operation for a day and replaced by the old methods of intermittent settling and decantation. Truly, the record is one of "distinguished achievement in non-ferrous metallurgy" that deservedly ranks the medalist with those who have preceded

Jan 1, 1930

By Francois E. Heuze

This paper summarizes the geomechanics programs conducted in two hard rock underground mining operations in the Western United States, between 1966 and 1981. The two projects were directed towards understanding the behavior of the rock masses, at the scale of the caverns. To this end, the emphasis was put on large scale field measurements, complemented by limited laboratory testing. The results of these observations were used to build realistic finite element models of the underground chambers. In the marble mine, at Crestmore, California, the models were applied to the structural optimization of the room-and-pillar pattern. In the granite mining, at Climax, Nevada Test Site, the models explained some unusual stress changes observed during excavation. Based on the large number of geomechanical techniques employed, specific conclusions and recommendations are offered regarding the quality, applicability, and usefulness of the various methods. The two case histories clearly indicate chat numerical models are extremely useful for a detailed understanding of the structural behavior of mine openings. To be realistic, these models must be based first and foremost on large scale field observations. The lessons Learned on these two projects also are directly applicable to the design and analysis of nuclear waste repositories in hard rocks such as basalt, granite, and welded tuff.

Jan 1, 1982

By Luiz C. Correa da Silva, Robert F. Mehl

A. D. Le Claire and R. S. Barnes (Atomic Energy Research Establishment, Harwell, Didcot, Berks., England)-—This much awaited paper admirably confirms that the Kirkendall effect is a true diffusion phenomenon and likely to be found in all diffusing systems. The most likely explanation put forward so far to account for the shift of interface is that the two components of the system, diffusing in opposite directions, do so with unequal rates so that there is a net loss of material from that half of the diffusion zone rich in the more rapidly diffusing component. This loss is accompanied, and at least partly compensated for, by a closing up or decrease in volume of this latter half of the diffusion zone and an expansion of the other half so as to tend to keep constant the overall volume per atom. This is manifest as a movement of the original interface. If this is a true picture of what is taking place then there are at least two important matters requiring further study."1—The quantitative relating of the observed shift with the independently measured separate diffusion coefficients of the two diffusing species."2—A detailed study of the mechanism and characteristics of the closing up process."We would like first to make a few remarks pertinent to these topics. In connection with the first of these, it is a pity that more and detailed measurements were not made on the Au-Ag system, the only one for which the separate diffusion coefficients of the two species have been measured.'" One of us (A. D. Le C.) has calculated from Johnson's results the shift to have been expected in samples D.2 and D.3. Darken4 showed that the velocity v with which the markers move is related to the separate diffusion coefficients Dau, Dag, by the eauation:"dN"v = (Dag — Dau "dx"dN"where .is the concentration gradient at the mark-ax"ers. Under certain conditions,4, 20 it can also be shown that:"Xm"v = "2t"where x, is the total marker shift after time, t:"dN". . xm = 2t (Dag — Dau) [9]"dX"Johnson measured Dag and DAu in a chemically homogeneous alloy and so his reported figures represent the true or ideal diffusion coefficients"; the same quantities in eq 9 represent the actual diffusion coefficients as would be measured in the presence of a chemical concentration gradient, so we need to multiply Johnson's reported values of Dag and Dau by the"1 before insert-dlogN "ing them in eq 9. 7 is the activity coefficient of Ag at the concentration prevailing near the markers which we shall assume to be - 50 pct. The values of the thermodynamic factor for N = 0.5 and the temperatures at which D.2 and D.3 were annealed were obtained from thermodynamic data quoted by Darken.' aN/ax was computed from the coefficient of inter-diffusion of Au and Ag given by Johnson on the assumption that in the samples D.2 and D.3, the concentration distance curve could be represented by the standard equation:""No is the original difference in concentration between the two halves of the couple, and + is the error or probability function."aN/ax at x = 0 is then given by:"adN/dx "2/nDt"and we assume that this represents the concentration gradient at the markers, although it is probable that the figure is slightly high."When all the appropriate quantities are inserted in eq 9, we find that the expected shifts are: for D.2, 0.0134 cm and for D.3, 0.0119 cm."The agreement between these results and those

Jan 1, 1952

By S. R. Mitchell, M. C. Fuerstenau, A. M. Gaudin

The two principal attributes of a thickener pulp are its settling rate and the ultimate pulp density of the thickened mud. Testing for evaluation of thickening attributes of a pulp has usually been done batch-wise by placing the pulp in a one-liter glass graduated cylinder and noting the position of the boundary between clear liquor and mud as a function of time. Refinements in testing have included repulping a thickened mud to various dilutions and evaluating the settling rate on these various repulped muds. This is considered to make possible an estimate of the settling rate as a function of pulp density and therefore to pinpoint the slowest settling pulp which ought to be critical from the standpoint of thickener plant design. Finally, tests are sometimes made with model-size continuous thickeners of arbitrary size. In batch tests it is generally accepted that the behavior of a pulp is described by a curve such as the one shown in Fig. 1, in which the position of the boundary between clear liquor and mud (the mudline) is plotted against time. It has also been assumed that the initial settling rate (the slope of the line segment AB) is descriptive of the pulp and independent of the size and shape of the container. Where the settling rate is slower and clearly a function of time (portion CD of the settling curve), it has been assumed that the data are not of much use because of the intrusion of compacting phenomena. The next important datum is the height. PE, which is a measure of the so-called ultimate pulp density. This quantity is assumed to be characteristic of the pulp and independent of the container. When actual data are recorded, results are rarely exactly according to this theory and numerous deviations may be noted. For example, some pulps seem to require an appreciable delay before beginning to settle, as in line AF. This is spoken of as representing the need for an induction time for flocculation. It has seemed desirable to explore thickener data with a more sensitive charting tool than is afforded by the coordinates of Fig. 1. Instead of relating the position of the mudline to time, it has seemed desirable to relate the rate of descent of the mudline to time. This, in effect, amounts to charting the slope of the line in Fig. 1, or the derivative of its ordinates, against the same abscissas. Fig. 2 shows the new chart for the curve ABCDE of Fig. 1. When this new tool was applied to data obtained, for example, with sized clay pulps, astonishing differences appeared. Apparently the traditional tool conceals differences instead of revealing them, whereas the new method emphasizes them. It seems, also, that both charting methods have their uses. In this article attention is focused on the effects of pulp density and container height as they affect the settling behavior of flocculated suspensions of a sized kaolin. The thesis by M. C. Fuerstenau' gives more details than this summary, as well as some information about the effect of other variables. Sized fractions of kaolin were used, supplied through the courtesy of S. C. Lyons of the Georgia Kaolin Co. Large batches were made by agitation in a flotation machine and in a glass jar equipped with a mixer. The settling vessels were 2, 4, and 6-in. diam glass cylinders of various heights. Pulp Dilution: The effects of pulp dilution on sedimentation behavior are shown in Figs. 3, 4, and 5. Fig. 3 shows data on pulps ranging from 2.44 to 16.7 pct solids initial pulp density, flocculated with Separan and charted in the traditional manner. At least two of the lines appear nearly straight in their early sections, but neither of the others does. Each of the curves in this figure includes a region labeled

Jan 1, 1960

By J. Szekely, G. P. Martins

A formulation is given and a general analytical solution is presented for the problem of spherical phase growth in multicomponent systems. The results are valid for describing the rate of bubble growth in the absence of translational motion and, therefore, should be relevant to heterogeneous nucleation processes. Typical worked examples are given, which include bubble growth due to the simultaneous diffusion of hydrogen and nitrogen in molten steel, and the growth of CO bubbles in steel, due to the reaction: C + 0 = CO. The calculations predict that the presence of additional components would enhance the growth rate and also increase the absolute rate at which the individual components are transferred into the bubble. These findings should be relevant to degassing processes. THE problem of spherical bubble growth in the absence of translational motion is appropriate to the description of the heterogeneous nucleation and subsequent growth of gas bubbles while attached to a solid surface. Such problems are of considerable practical relevance to various vacuum degassing and steelmaking processes where bubble nucleation and subsequent growth play an important part in the overall reaction mechanism. A definitive formulation of spherical phase growth has been given in the now classical paper by Scriven1 and the analogous problem for solid phase growth has been discussed by Horvay,2 furthermore a thorough review of the relevant literature has also become available.3 All this previous work was concerned with one component or binary systems. The purpose of this paper is to show that the technique developed by Scriven may be generalized to alow the consideration of multicomponent systems. The results of this generalization would be particularly relevant, as gas bubble nucleation in the metallurgical systems previously mentioned frequently involves the simultaneous diffusion of several components. In the following a general formulation is given and typical worked examples are presented. FORMULATION Consider the growth of a spherical gas bubble due to diffusion in a quiescent liquid of infinite extent, as sketched in Fig. 1. The formulation of such problems requires the statement of the following conservation equations relating to the liquid phase: Equation of continuity Equation of motion Conservation of the diffusing species—Diffusion Equation. The following assumptions are made: a) The fluid is incompressible, quiescent, and of infinite extent b) The bubble is stationary, i.e., it undergoes no translational motion c) Spherical symmetry is observed throughout d) The mass diffusivity is constant e) Chemical equilibrium exists at the surface of the bubble, and any reactions occurring there are fast compared to the diffusion process f) Inertia and surface tension effects are neglected. Equations derived on the basis of these assumptions by previous investigators were found to provide a reasonable representation of bubble growth while attached to a surface in organic and aqueous systems4,5 For gas bubble growth in molten metal systems assumptions a) to d) chould hold reasonably well. The exclusion of chemical kinetics as a possible rate limiting step may not be universally valid, but should hold for many systems operating at high temperatures. The effect of hydrodynamic inertia may be neglected for moderate growth rates; finally, the assumption neglecting the effect of interfacial tension on the bubble growth was made for the sake of mathematical convenience; its inclusion would have required the use of quite cumbersome numerical techniques. While surface tension effects could be appreciable on the initial values of the overall growth rate, especially at low absolute pressures and in case of small bubbles, they are not thought to modify the relative effects present in multicomponent systems, the study of which is the objective of this paper. Within the framework of the above assumptions

Jan 1, 1970

By W. A. White

UNDERCLAY squeeze is the plastic flowing of underclay below coal pillars into mined-out entries and rooms. Squeezes may be caused either by wet mine conditions where the moisture is taken up by the clay—making it more plastic—or by the presence of certain clay minerals, such as mont-morillonite, which are plastic when there is enough natural moisture. Under either condition, sufficient stress will cause the underclay to flow. Squeezes may fill an entry or room within several hours, or it may be several months before movement stops. Squeeze areas commonly cover hundreds or thousands of square yards. The Coal Div. of the Illinois State Geological Survey has collected samples of underclays from various mines and from cores drilled by coal companies in the state. From these samples natural moisture content, particle size and particle size distribution, and clay mineralogy are determined. Data from samples collected from the underclay below Herrin (No. 6) coal in the Lumaghi Coal Co. mine near Collinsville, Ill., are used in this report to clarify points in the discussion. Data from samples taken from other mines lead to the same conclusions. A generalized geological section for the area is given in Table I. The underclay below coal No. 6 ranges from a few inches to 3 or 4 ft thick. The upper 6 to 18 in. are noncalcareous; the lower part becomes more calcareous with depth. Limestone nodules become larger with depth, almost grading into the limestone below. In areas where the clay is nearly absent the limestone may thicken to take its place; thus they may complement each other in thickness. There are two types of squeeze areas in a mine. In one type up to 3 or 4 ft of underclay lie in what appears to be a depression in the limestone underneath. This is suggested by a rim surrounding the squeeze area where the underclay is thin and the limestone lies within a few inches of the coal. In the second type the underclay of the squeeze area is surrounded by underclay of similar thicknesses which does not squeeze. Test Methods: Natural moisture content, particle size and particle size distribution, and clay mineralogy were determined by the following methods: Natural moisture is the moisture content a clay contains in its natural environment, expressed in percentage of the weight of ovendried clay (110°C or 230°F). To obtain the natural moisture content, given in Table 11, the clay samples were sealed in containers as soon as the samples were taken in the mines. Particle size and particle size distribution were determined by the pipette method,' and the data were plotted as cumulative curves, Fig. 1, on semi-logarithmic paper. Particle size was plotted on the logarithmic scale and percentage on the arithmetic scale. The quartiles (diameters that correspond to frequencies of 25 and 75 pct) and medians (diameters that correspond to the frequency of 50 pct) of the samples were determined from these curves. The clay minerals were identified from the data obtained by differential thermal' and X-ray powder" techniques. The differential thermal analyses were made on the whole samples, whereas the X-ray analyses were made on fractions of less than 2p. Data and Discussion Moisture Content: After the sealed jars had stood for 24 hr, those that contained squeeze samples had perspired, so that droplets of water had accumulated on the insides of the jars. Table II shows the moisture in the clay after it had perspired for 24 hr. (This perspiring was not noted in samples from nonsqueeze areas.) After perspiration one of the squeeze samples still had a higher moisture content than the samples that did not squeeze. Clay Mineralogy: The thermal analysis, Figs. 2 and 3, indicates that the clay minerals are chiefly micaceous in type; the low-temperature endothermal

Jan 1, 1957

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,' and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson' determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12'13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By Ken-ichi Hirano, B. L. Averbach, Morris Cohen, N. Ujiiye

The influence of plastic deformation in compression on the self-diffisivity of a iron has been measured in the temperature range of 742º to 885°C. The diffusivity is enhanced in proportion to the strain rate, but this dependence decreases with increasing temperature. The magnitude of the strain is relatively unimportant in this connection. Strain rates from 0 to -2 x 10-3 sec-1 were investigated, with a corresponding increase in diffusivity up to 3 x 103 times. The results are analyzed in terms of vacancy diffusion and the excess vacancies introduced during dejornzntion. It is concluded that grain boundaries are the main vacancy sinks in polycrystalline iron and that the vacancy lifetime is therefore dependent on the grain size. A typical vacancy lifetime at 800°C with a nzean grain-boundary intercept of 0.3 cm is of the order of 1 sec. LATTICE imperfections are considered to be the dominant mechanism of diffusion in close-packed crystals. Vacant lattice sites are usually the most important defect, but the enhancement of diffusion along grain boundaries and other short-circuiting paths has been well documented. Inasmuch as plastic straining produces a variety of defects, it would be expected that the application of stresses sufficient to cause plastic flow during a diffusion run might result in an increase in the self-diffusivity. Enhanced self-diffusion in a iron under compressive creep has been observed by Buffington and Cohen' and subsequent coworkers.2 Lee and Maddin3,4 have also found an enhancement in the self-diffusivity of silver single crystals undergoing torsional deformation. On the other hand, Darby, Tomizuka, and Balluffi5 have not observed any significant diffusion increase in single crystals of silver deformed either in tension or in compression, although the results in this case may have been affected by the occurrence of recrystallization. With poly crystalline silver, however, Forestieri and Girifalco6 have found en- hanced diffusion during compressive creep. A small decrease in the self-diffusivity of zinc single crystals under compressive loading has been reported,7 but the applied stresses in these experiments were too low to cause appreciable plastic deformation. For the cases in which enhanced diffusion has been found, a number of common effects have been noted. Usually, the ratio of the diffusivity during straining, Ds, to the diffusivity in the unstrained condition, D,, varies linearly with the strain rate, and does not seem to be a function of the plastic strain, at least up to ? = 0.2. Values of Ds/Du of the order of 100 have been reported'-4 but the enhancement decreases with increasing diffusion temperature. The activation energy for diffusion decreases markedly with increasing strain rate and approaches a level of roughly one-half the unstrained value. Most of the current explanations of these observations assume that excess vacancies are generated by the deformation, but rather large concentrations of excess vacancies and/or long lifetimes are required by these theories.',',',' Since the original work on iron, there has been an important improvement in the compressive-loading technique.2 The early data were also analyzed without taking into account the motion of the coordinate system in the specimens undergoing plastic deformation. This problem has now been solved by a number of investigators (see Refs. 11, 12, and the appendix of the present paper). Consequently, the strain-diffusion runs on iron for the Ds measurements were repeated and extended over wider ranges of temperature and strain rate. In addition, the original diffusivity data9 on the unstrained iron have been corrected for the divergence of the beam in the counting system and new data points have been added, resulting in somewhat different values for the self-diffusi-vities in a iron.10 The new values for Du are used in this paper. A comparison of Ds and Du confirms the large enhancement in the self-diffusivity of iron during compressive creep, as previously reported.',2

Jan 1, 1963