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By J. Chipman, J. C. Fulton

Reduction of Si from slag to carbon-saturated iron is a very slow reaction. The rate is nearly independent of stirring but is accelerated markedly by increased temperature. In a slag containing 45 pct SiO2, 38 pct CaO, 17 pct Al2O3, the energy of activation is approximately 130 kcal. AT temperatures of 1450" to 1600°C occurring in the hearth of the iron blast furnace, chemical reactions are normally expected to proceed with great rapidity. Many of the reactions of iron making are indeed quite rapid and attain a condition corresponding roughly to a state of equilibrium before metal and slag are tapped from the furnace. The one conspicuous exception is the reaction by which carbon in the coke or metal reacts with silica in the slag to deliver silicon to the metal. From the practical viewpoint the slowness of this reaction is indeed fortunate, for if it were fast enough to reach equilibrium during the time of contact, it would be difficult to produce pig iron of the desired low silicon content. The one other reaction which under certain circumstances can also be very slow is the transfer of sulfur from blast-furnace metal to slag. In their laboratory exeriments on this reaction, Hatch and Chipman found that at least 5 hr were required for the attainment of equilibrium in a small crucible and that the reaction was not accelerated by increasing the rate of stirring. Subsequently it was shown2 that the presence of a reducible oxide MnO greatly inhibited sulfur removal, and finally that SiO2 itself3 under some conditions has sufficient oxidizing Dower to interfere with sulfur transfer. The kinetics of sulfur removal are now rather well understood,4 and it has been shown3,5 that when the silicon content of the metal is high enough to prevent reduction of SiO,, the desulfurizing process is rapid. Thus the observations of slow removal of sulfur are associated with the coincident slow reduction of SiO2, a process which transfers both silicon and oxygen to the metal phase. It is, of course, the oxygen which interferes with sulfur removal. An explanation of the slowness of the silica reduction reaction has not been obtained. The sulfur transfer process has been shown by the authors5 to be at least partially transport-controlled in the absence of interference by silica. Under the experimental conditions. 99 pct of the total transfer at 1600" was accomplished within an hour. Under similar conditions the reduction of silica may not proceed half-way to equilibrium6 in 8 hr. It is scarcely imaginable that silica reduction could be transport-controlled when the slag contains 44 pct SiO2 and the metal about 1.4 pct C. The experiments reported here show definitely that it is controlled by a slow step or steps in the chemical reaction. One might expect to find such a slow step in the breaking of SiO bonds or in the slow removal of oxygen by carbon at the slag-metal or metal-crucible interface or by bubble formation. EXPERIMENTAL PROCEDURE The experimental procedure used in this investigation was similar to that used in the study of the kinetics of desulfurization.5 A sketch of the graphite crucible and stirrer used in the current work is shown in Fig. 1. The quantity of metal and slag used was adjusted so that the slag-metal interface was located between the top and bottom blades on the stirrer; the top of the slag layer was above the top blade. The stirrer shaft was hollow down to the metal level and served as thermocouple well or optical pyrometer target. Stirring speeds of 0 to 500 rpm were used. A carbon monoxide atmosphere was maintained in the furnace by flushing the gas over the slag surface, except in run No. 220 when it was bubbled

Jan 1, 1960

By P. M. Kelly, E. P. Butler

The stability of a 70/30 Mn-Cu alloy aged to peak damping has been investigated using electron microscopy, X-ray diffraction, and torsional pendulum measurements. Storage at room temperature or at 100" C causes a reduction in damping capacity. This is shown to be due to the formation of subdomains which "lock" the main domain structure and so hinder their movement. After storage the damping capacity can be restored by a retransformation treatment, which generates structures identical to those found in newly aged specimens. Plastic deformation by rolling also causes a decrease in damping capacity. In this case the damping capacity can only be restored by retransformation if the amount of deformation is less than about 5 pct. THE general metallography and structure of these high damping capacity alloys has been discussed in Part I of this work.1 Part II deals with some of the variables that affect the damping capacity. In particular, the stability of the damping capacity of a 70/30 alloy aged for 2 hr at 425° C and quenched has been investigated. The temperature sensitivity of the damping capacity of a 70/30 alloy aged for 2 hr at 450° C has been reported by Birchon.2 The damping capacity begins to decrease with increasing temperature, and is very low above the M, temperature of 125°C. The cubic — tetragonal transformation is completely reversible and there is no apparent thermal hysteresis associated with the change in damping capacity. Another important effect was first reported by Dean and his coworkers.3 They noticed a decrease in the damping capacity with time for specimens of a quenched tetragonal alloy. More recently workers at the Admiralty Materials Laboratory 4 have studied the stability of an aged 70/30 alloy. They found that the damping capacity decreased to half its original value after about 1000 hr at room temperature. EXPERIMENTAL The techniques used for electron microscopy and X-ray diffraction have been described in Part I. The damping capacity was measured by means of a torsional pendulum, using rectangular specimens, 3 by 0.3 mm with a 6 cm gage length. The specific damping capacity, S.D.C., was calculated as a percent amplitude decay in free vibrations over 10 cycles, starting at an amplitude which corresponded to a 700 psi surface shear stress. Because of the stress dependence of the damping,' the values obtained were about a third those reported for a 5000 psi surface shear stress.' RESULTS a) Effect of Aging Temperature. The effect of aging temperature on the damping capacity is shown in Fig. 1. The damping capacity reaches a peak of 12 pct after aging at 400° to 425°C) then begins to decrease as the volume fraction of a Mn increases. At higher aging temperatures the structure becomes cubic again with a low damping capacity. b) Stability of the Aged Structure. The damping capacity of the aged alloy decreases with time at room temperature. This process could be accelerated by storing at 100°C, when about 100 hr were required for the damping to fall to half its original value. The results of room temperature and 100°C storage, for times up to 1000 hr, are shown in Fig. 2. The damping capacity starts to decrease after about 24 hr at 18° C and 1 to 2 hr at 100°C. It was found, however, that the damping could be almost completely restored by retransformation. The specimens were held at a temperature above the M, for a short time, 250° C for 5 min, and then quenched. The values of damping capacity for specimens that were aged, stored, and then retransformed are shown by the full points in Fig. 2. X-ray measurements of the c/a ratio and hardness readings on the specimens did

Jan 1, 1969

By J. Spreadborough, D. LaW. King, E. Anderson

Tmzsile tests were performed on Armco iron samples, at various ternpe.ralures and strain rates, ocer a wide range of grain sizes. Analysis of the data suggests that the plot of the lower yield stress, against d-1/2,where 2d is the acerage grain diameter, is not linear (as is often assumed) but is concave toward the d. axis over the range of d-from 7 to 53 . The different values of the parameters obtained by other workers can be explained, in part at least, by the observed curvature. This curvalure is shown to be consistent with a model of yielding based on dislocation pile-ups; however, the values of obtained by fitting our data to this model differ appreciably from the values generally reported. The equation proposed by Cottrell, viz.: is a plausible empirical fit to the experimental results. The purpose of this paper is to comment on the validity of the widely used linear relationship first proposed by all' and Petch and coworkers2"4 between ay, the lower yield stress, and 2d, the average grain diameter, for bcc metals, viz.: Many workers, see Refs. 2 to 7 and Table 11, have fitted this equation to their experimental results and have obtained acceptable fits over the relatively narrow range of grain sizes used by most of them. Indeed, in some cases, so few data points were available that any more sophisticated fit would have been irrational. In most of the interpretations,'-' oi is thought to be a measure of the friction stress accompanying dislocation movement, and ky was originally inter- preted as a measure of the dislocation locking but is now believed by Cottrell" to be a function of the dislocation creation rate. In the "unpinning" theories, k, is equated to where od is the unpinning stress and 1 is the average distance from the boundary of the grain where yielding is taking place to the nearest dislocation source in an unyielded grain. Other considerations (see, for example, Refs. 11 and 12) lead to equations with a similar form to [I] where different meanings may be attributed to the parameters. While there are doubts as to the physical significance of the parameters i and k, they continue to be used by many workers; interpretations of the variations in the behavior of ferrite materials following certain treatments, e.g., aging,'3 neutron irradiation,14 have been given frequently in terms of these parameters. Some theories of the mechanical behavior of bcc metals are based on this relationship. We have investigated experimentally the oy - d-'lZ relationship for Armco iron over a wider range of grain sizes and with more data points than those given in published results. The analysis of our data suggests that the oy—d-'" relationship is not linear but is in fact concave towards the d-'I2 axis. RESULTS AND DISCUSSION The experimental work was carried out on 3-mm-diam Armco iron rods which were prepared by wire drawing from 5-mm-diam rods. By annealing in vacuum at temperatures between 7000 and 1200°C for various times, grain sizes from 7 to 20,000 grains per sq mm were obtained, the grains in all cases being regularly shaped. Grain sizes were measured by lineal interceptand by area methods; only specimens with Amax/A values of 3 to 6 were used in the Petch-Hall plots (where A is the average area of a grain and Amax is the area of the largest grain observed). For all the specimens used, the number of grains in a cross section exceeded 50, which should be adequate to avoid grain size effects.'= Tensile tests were performed at 296", 219, and 17l°K, using

Jan 1, 1969

By G. A. Vissac

The only fine coal washer with proved automatic controls, the feldspar jig is capable of good efficiencies even at low separating gravities, handles a variety of products, and treats 150 tph and over. IN continental Europe the feldspar jig is used almost exclusively for cleaning the fine sizes of coal; it operates with an artificial bed, made up generally of pieces of feldspar or of any other hard and heavy rock with good cleavages. A primitive form of this machine requiring close supervision was used in this country years ago, but output was small. The modern machines are generally air-pulsated Baum-type jigs, with capacities up to 150 tph, and treat sizes from % in. to 0, usually previously dedusted or deslimed. These jigs are equipped with very accurate and sensitive automatic controls insuring satisfactory operation even at low separating gravity and with feeds irregular in quality and quantity. This paper will deal more particularly with coal cleaning separation, but the technical studies apply equally to all minerals. Theory of the Feldspar Jig To understand fully the operation of the feldspar jig and to appreciate its potential value, it is necessary to measure and analyze the motion of small particles of various specific gravities, falling in various media, under various conditions. As no practical formulas were available for that purpose, the writer has developed new theories and established new sets of formulas, which cannot be demonstrated here. They are applicable to all minerals and to many problems of coal or mineral concentration. These formulas do not pretend to absolute accuracy, but results, tested by comparison with experimentally recorded data, are sufficient for practical purposes, as they give definite indications of trends, relative values, and order of magnitude of the many factors involved. For pulsating motions no earlier formulas are available. In the case of continuous currents or motions, such formulas as Rittinger's, Allen's, or Stokes', over a hundred years old, apply only to special shapes and sizes of particles, involve factors and coefficients difficult to measure or appreciate, and deal only with free motions. They are of little use in solving practical problems. Units used with the formulas presented here are in the CGS system. Lateral friction and suction have been taken into account according- to methods currently used in aerodynamics, and only hindered motion is dealt with. As the feldspar jig is primarily intended to create a fluid bed condition, the mixture of fluids and solids obtained is homogeneous, and the apparent specific gravity of the separating medium is calculated accordingly. For instance, if 20 pct of the volume is coal and shale, with an average of 1.60 sp gr, in a liquid of 1.10 sp gr, the actual specific gravity of the separating fluid is 0.80 x 1.1 + 0.20 X 1.6 = 1.20. The fundamental equations are as follows: The general motion of a particle falling in a medium of specific gravity equal to u, hindered motion. is dv/dt = g/Ls [ L (s-u) - u/g v2 [1] g = 981 cm per sec, acceleration of gravity, and L = thickness of the particle of specific gravity (s) and velocity (v). The initial acceleration dv/dt = g (1-u/s ) [2] is a function of the specific gravity of the particle, only for a given medium, and independent of its dimensions—an ideal separating condition. The terminal velocity Vt = gxL- (s-u)/u, [3] for a given value of u, is a function of s and L. Two particles, L, s, and L2 s2, are said to be equivalent if they have the same terminal velocity, and accordingly L1/L2=s2-u/s1-u. [4] Two such particles cannot be separated by continuous currents, in any concentrating device. Because the initial accelerated motion, which provides for efficient separation, is followed by a constant velocity, which has a limiting effect, it is essen-

Jan 1, 1956

By Rex B. McLellan, W. A. Oates

FROM a consideration of the application of the Gibbs-Duhem equation to multicomponent systems arken' derived the following equation applying to dilute solutions of a solute, 2, dissolved in a binary solution, 1-3:

Jan 1, 1969

By T. S. Spice, H. L. Lovell, R. W. Utley

With the increased demand for lightweight aggregate, such materials have been manufactured from slags, clays, slates and, to a minor extent, the refuse of coal preparation processes. The latter source is attractive due to current interest in eliminating air pollution and improving the unsightly appearance of refuse piles as well as potential economic advantages, if a satisfactory product can be manufactured. A study has been made relating the composition of coal refuse, expressed as washability data, and the properties of a resulting aggregate. Three different refuse samples (bituminous and anthracite) were separated at gravities ranging from 1.4 to 2.96. Their chemical composition was determined. Aggregates were prepared in the laboratory from these fractions before and after ashing, at temperatures between 1250' and 1350°C. The specific gravity, expansion and compressive strength of the products were measured. The response of the refuse to bloat is related to the chemical composition of the ash to yield a glass of desirable viscosity and to the presence of a material which will form a gas in the appropriate temperature range. Carbonaceous material within the particle is a negative factor since after the glassy phase forms, oxygen cannot enter the mass thus inhibiting bloating. Precombustion of the refuse is also detrimental since it removes substances of gas-forming capability. The fraction sinking at 2.60 yielded an aggregate which had the lowest specific gravity, greatest expansion and greatest compressive strength. The purpose of this study was to seek and evaluate possible relationships between the composition of coal refuse, as expressed by washability data and factors affecting the production of a lightweight aggregate from refuse by bloating. The study was related to an intense program in the Department of Mineral Preparation at the Pennsyl- vania State University to study the possible elimination of air pollution from coal refuse fires by producing a low-carbon secondary refuse. Another phase of this program is considering possible uses of such a secondary refuse. Thus one study was to determine if a lightweight aggregate could be produced from this new refuse material and what effect the nature of refuse beneficiation would have upon the characteristics of a commercial aggregate product. It was hoped that these studies would assist in the design of a process and in establishing the optimum specific gravities at which refuse separation could be made in respect to the production of a low grade fuel from the float product and a raw material for lightweight aggregate from the sink product. The combination of producing a saleable low grade fuel and a lightweight aggregate, while at the same time minimizing disposal costs and air pollution contributions would be attractive to the coal mining industry. MECHANISM OF BLOATING Austin, Nunes and Sullivan,1 Ehlers,3 Everhart, 4 Riley7 and others, have stated that bloating is an expansion process in which two essential conditions exist simultaneously. These are: the development of a glassy phase over a relatively wide temperature range (the viscosity of this glassy phase plays a major role in the retention of the evolved gases) and the evolution of gases (SO2, SO3, CO2 and O2) from mineral decomposition in sufficient quantities at appropriate temperatures to form a cellular structure in the mass. Unless these two "type" reactions take place at the same time or in overlapping ranges of time and temperature, cellulation will not occur. In this event, the gas will escape or the melt will be too fluid to retain it; or if retained, the cells may be too large or the walls too thin for good strength in the product. The stages that occur when clays and shales are heated in an oxidizing atmosphere may be summarized as follows: 1) Drying and removal of free water to 200°C. 2) Absorbed water dehydration period (200 to 480°C). 3) Chemically-combined water dehydration period (480 to 700°C).

Jan 1, 1965

By C. H. Li, J. A. Sarteli, W. Bonfield

The stress to cause a permanent micros train of 2 x 10-6 in. per in. (defined as the microscopic yield stress) in beryllium is found to be very sensitive to surface condition. The initiation of plastic flow in as-machined specimens, which contain a high density of twins and large residual compressive stresses to a depth of about 0.010 in. from the surface, occurs by the nucleation of slip from high stress fields around twin tips in the surface layers. Removal of the damaged surface layers by chemical polishing results in an appreciable increase in the microscopic yield stress, which is attributed to the remoual of stress raising twins rather than to the release of residual stresses. IT is well known that the macroscopic mechanical properties of beryllium are very sensitive to the nature of its surface finish. Matthews and coworkers1 have shown that the tensile strength of rolled beryllium sheet can be considerably enhanced by chemical polishing, presumably due to the removal of the high concentration of notches, twins, and large residual compressive stresses normally found in the surface layers of ground specimens. There was no similar effect of surface condition on the macroscopic yield stress (the stress to produce 0.2 pct strain), a point to which we shall return. To date there have been no extensive studies on the effect of surface condition on the microstrain region of beryllium. Recent measurements2 of the stress to cause a permanent microstrain of the order of 10-6 in. per in. on machined hot pressed QMV beryllium, gave values ranging from about 600 to 3500 psi. Reasons for the considerable scatter in the results were not discussed. In this paper, we wish to show that the microstrain region of polycrystalline beryllium is, in fact, very sensitive to surface condition. The stress to cause a permanent strain of 2 x 10-6 in. per in. which for convenience we will refer to as the microscopic yield stress, can be increased by almost a factor of 2 by minimizing the amount of surface damage. The variation of microscopic yield stress is attributed to the presence of twins in the surface layers, rather than to residual compressive stresses. EXPERIMENTAL PROCEDURE The starting material for this investigation was commercial purity hot pressed QMV beryllium, with an average grain size of about 20 . The effects of surface treatment were assessed by comparing the microstructure with residual stress measurements and microstrain properties. Specimens were prepared for metallographic examination by wet grinding with 240, 400, and 600 papers, followed by polishing with a suspension of fine alumina in warm 20 pct oxalic acid. After this treatment, the surface could be examined, either in the unetched condition with polarized light, or after etching in 2 pct hydrofluoric or boiling 20 pct oxalic acid with normal light. Thin films of beryllium suitable for electron transmission study were prepared from bulk specimens by chemical polishing with hydrofluoric and phosphoric acids, and were examined in an RCA-EMU-3 electron microscope. Residual stress measurements were made by a procedure similar to that of Treuting and Read.3 Specimens 4.0 in. by 0.625 in. by 0.080 in. were prepared by three different machining procedures, namely: turning, grinding, and sawing, in order to introduce different levels of residual stresses. An electrical resistance strain gage was attached to one side of the specimen, and that surface was then protected by an acid-resistant enamel, while the opposite surface was removed by etching approximately one thousandth of an inch at a time. The change in specimen curvature in the longitudinal direction was noted and the residual stress was calculated by the following formula:

Jan 1, 1963

By Oscar Weiss

STILFONTEIN and surrounding areas gave nega-tive results in all prospecting attempts since about 1904 when Goerz and Co., a forerunner of Union Corporation Ltd., first drilled in the region and on the farm Stilfontein. Subsequent efforts by African and European Investments Co. and Anglo American Corp. from 1934-37 were completely unsuccessful. Holes drilled by these companies on the farms Riet-fontein, Hessie, and Palmietfontein were stopped in the Lower Witwatersrand system without finding payable reefs. The results of gravimeter, ground magnetometer, and aerial magnetometer surveys are presented in the area, in and around the new Stilfontein Gold Mine, in the Klerksdorp District of the Transvaal in the Union of South Africa. The gravimeter and ground magnetic surveys were completed in 1947—48. The gravity anomalies suggested a block of Upper Witwatersrand quartzites faulted-up between denser rocks of dolomite and Ventersdorp lava. Boreholes S.T. 1, 2, and 3 were drilled in 1948 and, after penetrating the dolomite and Ventersdorp lava, entered Upper Witwatersrand quartzites and intersected the Gold Estates Reef and Vaal Reef. Subsequent drilling delineated the suboutcrop of the Vaal Reef and determined the main structure of this horizon. The gold content of the Vaal Reef was highly payable and shaft sinking is now in progress. The Stilfontein Gold Mining Co. has been formed and, up to date, f5,000,000 capital has been raised for plant, shaft sinking, and development. The payable Vaal Reef horizon extends further south from Stilfontein, the reef occurring at increasing depths. It is possible that at least another mine may be established on these deeper horizons. The farm Stilfontein 39 is situated in the Klerksdorp District of the Transvaal. This farm and the surrounding areas have been subjected to repeated programs of prospecting dating back to about 1904, when Goerz and Co., the forerunner of Union Corporation, Ltd., first drilled on the farm and in the surrounding areas. From 1934-37, numerous boreholes were drilled on the neighboring farms, Riet-fontein. Hessie. and Palmietfontein, by African and European Investment Co. and Anglo American Corp. All these efforts were completely unsuccessful, and nobody suspected any possible gold-bearing area on Stilfontein until about 1947, when a gravity traverse run by B. D. Maree on the main road, showed a negative gravity anomaly. During 1947-48, the writer's organization completed gravimeter and magnetic surveys on Stilfontein and Rieffontein. An area of negative gravity anomalies was mapped, and it was suggested that this could be caused by blocks of Upper Witwatersrand quartzites, of the average density of 2.65, faulted up between dolomites and Ventersdorp lavas, the density of both of these rocks being 2.8. Fig. 1 shows the geology of the area as mapped by L. T. Nel of the Geological Survey of South Africa. The boreholes on Stilfontein, with the exception of a single hole of Goerz and Co., were drilled after the completion of the geophysical survey. The grouping of the first boreholes S.T. 1, 2, 3, 4, 5, and 6, clearly shows that these were located in the zone of negative gravity anomalies. Fig. 2 shows the gravity anomaly contours. Fig. 3 shows two sections across the gravity anomaly, together with the corresponding geological sections as obtained from boreholes. The close relation between gravity values and thickness of dolomite plus Ventersdorp lavas is striking. The two latter formations having the same density (2.8), act as one mass as far as gravity effects are concerned. Fig. 4 shows the magnetic anomalies observed on the ground by vertical magnetometers and at 500 ft abbve mean ground level by aerial magnetometer. The latter are anomalies of the total magnetic intensity. The magnetic results show that, on the farm Rietfontein and on the northern half of Stilfontein. Lower Witwatersrand magnetic shales were to be expected at relatively shallow depths. As the strongly

Jan 1, 1952

By Rex B. McLellan, W. A. Oates, William W. Dunn

Vapor transport experiments have been carried out in order to determine the saturation solubility of carbon in cobalt and nickel with respect to graphite over a large temperature range. Some of the uncertainty existing in the thermodynamics of these systems has been removed and accurate estimates of the heat and entropy of solution of carbon in nickel and cobalt have been deduced. The relatitle partial entropies of carbon are considered to be predominantly vibrational in origin. ALTHOUGH the thermodynamic properties of solid solutions of carbon in cobalt and in nickel have been investigated previously, the results of these investigations show a marked lack of agreement amongst themselves. In this investigation simple vapor transport experiments have been undertaken in order to measure the temperature variation of the saturation solubility of carbon in nickel and cobalt with the object of removing to some degree the uncertainties in the thermodynamics of these systems. In the case of the C-Co system, early measurements of the saturation solubility of graphite in Co show results at the same temperature differing by almost an order of magnitude.1-5 Recently Schenck, Frohberg, and Jaspert6 measured the equilibrium between CH4-H2 mixtures and C-Co solid solutions at five temperatures ranging from 850° to 1050°C. Their values of the activity of carbon in the solid solution, deduced from a knowledge of the chemical potential of carbon atoms in the gas, varies linearly with composition at each temperature and the authors concluded that the solutions were Henryan. The saturation solubilities deduced from Schenck, Frohberg, and Jaspert's measurements are in good agreement with the solubility determined at 1000°C by Rao and Nicholson7 and the value at 1000°C deduced from the measurements of smith8 on the equilibrium between CO/CO2 mixtures and C-Co solutions. The object of this investigation was to check the results of Schenck, Frohberg, and Jaspert and also to extend the range of solubility data to higher temperatures. In the case of the C-Ni system, there is fairly good agreement between the values given by schaefer9 for the saturation solubility of carbon C, in nickel, the value given at 1000°C by Rao and Nicholson,7 and that deduced from Smith's8 measurements of the equilibrium between C-Ni solutions and CO/CO2 mixtures at 1000°C. The values of C, deduced from Schenck, Frohberg, and Jaspert's6 measurements of the carbon activity in nickel are also in fairly good agreement. However, there is a large discrepancy between the above set of measurements and those of Lander, Kern, and Beach," who measured the carbon solubility of nickel in equilibrium with graphite by depositing an excess of graphite on the surface of Ni-foils from a gaseous mixture and subsequently diffusing in the carbon. These results are considerably higher than those mentioned above. The determinations6 of carbon activity a, in nickel from the CH4-H2 equilibrium showed that at all the temperatures investigated, the ac-values varied linearly with concentration up to about a, = 0.6 and then began to increase with concentration much more rapidly. On the basis of auxiliary experiments in which C-Ni solutions were equilibrated with graphite, Schenck, Frohberg, and Jaspert concluded that their CH4-H2 solid equilibrations at high values of a, were spurious and a, behaved linearly with composition up to the saturation limit (a, = 1). The short linear extrapolations of Schenck, Frohberg, and Jaspert's a, data yield values of C, in good agreement with those of Lander, Kern, and Beach." The solubility data for nickel discussed here is presented in Fig. 1 in the form of plots of ln[Cc/(l - 2cc)] vs 1/T. The discrepancies mentioned are clearly seen. In this investigation a vapor transport method is used to measure C, over as wide a temperature range

Jan 1, 1969

By D.E. Norquist, J. E. Moeller

The results of wear on marked balls, 4, 31/2, 3, and 2 in. diam are given. All balls were forged steel of practically the same chemical analysis and hardness. The results indicate that balls in a given mill for a given length of time will have equal diameter losses, regardless of size. IN order to determine the relative wear rates of several sizes of grinding balls, groups of 4, 31/2, 3, and 2 in. balls were marked individually and were charged, all at the same time, into each of two production mills grinding copper ore. The remainder, and vast majority, of the ball charge consisted of 2 in. diam, and smaller, white, cast iron balls. The original weight of each test ball was determined and recorded. Some of each group of test balls were recovered from the mills periodically, individually reidentified, and reweighed. The test balls were recovered during regular maintenance shutdowns, at approximately thirty-day intervals, so as to avoid disrupting operations. As soon as the weights had been recorded, each marked ball was recharged into the mill from which it had been taken. The test units were mechanically the same and theoretically received equal tonnages of feed. All of the test balls were of forged, alloy steel composition with only slight variations in chemistry that would not be expected to affect the physical properties. All were heat treated in the same manner to produce a high hardness, as equal as possible for all sizes and as uniform as possible from surface to center. Generally speaking, the hardness of the portion worn from the balls during the test ranged from 62 to 65 Rockwell C. The microstructure was, therefore, predominately martensitic. The method of marking the test balls consisted of forming a small, round hole, 3/16 or 1/4 in. diam, into the center of each test ball with a Thomas Metal Master disintegrator, which produces a hole in fully hardened steel without affecting the hardness of the surrounding metal. After the hole was formed, each test ball was individually weighed to the nearest gram and the weight was recorded. The balls were grouped as to size and each group assigned a code letter. The individual balls within the various groups were then assigned a number. A small copper disc was stenciled on one side with the group letter and on the other side with the individual ball number and dropped into the hole in the corresponding test ball. The hole was then plugged with a low-melting-point metal alloy, which could be melted out in boiling water. Half of the test balls in each group were charged into one mill and the other half into another mill, so that all test balls in each mill would be subject to, as nearly as possible, identical conditions for an equal length of time. Previous testing had indicated that the wear rates on balls of different sizes could not be accurately compared if weight loss, or percentage weight loss, were used as a basis for comparison. Fig. 1 is a graphic record of the average weight loss for each size group in mill No. 1, and it becomes readily apparent that the larger balls lose substantially more weight in a given length of time. Fig. 2 is a graphic record of the average percentage weight loss for each size group in mill No. 1, illustrating that the smaller balls definitely lose a greater percentage of their original weight in a given length of time. It was, therefore, decided to convert the actual weights of the test balls to diameter and follow the diameter losses periodically to see if the wear rates

Jan 1, 1951

By D. E. Norquist, J. E. Moeller

The results of wear on marked balls, 4, 31/2, 3, and 2 in. diam are given. All balls were forged steel of practically the same chemical analysis and hardness. The results indicate that balls in a given mill for a given length of time will have equal diameter losses, regardless of size. IN order to determine the relative wear rates of several sizes of grinding balls, groups of 4, 31/2, 3, and 2 in. balls were marked individually and were charged, all at the same time, into each of two production mills grinding copper ore. The remainder, and vast majority, of the ball charge consisted of 2 in. diam, and smaller, white, cast iron balls. The original weight of each test ball was determined and recorded. Some of each group of test balls were recovered from the mills periodically, individually reidentified, and reweighed. The test balls were recovered during regular maintenance shutdowns, at approximately thirty-day intervals, so as to avoid disrupting operations. As soon as the weights had been recorded, each marked ball was recharged into the mill from which it had been taken. The test units were mechanically the same and theoretically received equal tonnages of feed. All of the test balls were of forged, alloy steel composition with only slight variations in chemistry that would not be expected to affect the physical properties. All were heat treated in the same manner to produce a high hardness, as equal as possible for all sizes and as uniform as possible from surface to center. Generally speaking, the hardness of the portion worn from the balls during the test ranged from 62 to 65 Rockwell C. The microstructure was, therefore, predominately martensitic. The method of marking the test balls consisted of forming a small, round hole, 3/16 or 1/4 in. diam, into the center of each test ball with a Thomas Metal Master disintegrator, which produces a hole in fully hardened steel without affecting the hardness of the surrounding metal. After the hole was formed, each test ball was individually weighed to the nearest gram and the weight was recorded. The balls were grouped as to size and each group assigned a code letter. The individual balls within the various groups were then assigned a number. A small copper disc was stenciled on one side with the group letter and on the other side with the individual ball number and dropped into the hole in the corresponding test ball. The hole was then plugged with a low-melting-point metal alloy, which could be melted out in boiling water. Half of the test balls in each group were charged into one mill and the other half into another mill, so that all test balls in each mill would be subject to, as nearly as possible, identical conditions for an equal length of time. Previous testing had indicated that the wear rates on balls of different sizes could not be accurately compared if weight loss, or percentage weight loss, were used as a basis for comparison. Fig. 1 is a graphic record of the average weight loss for each size group in mill No. 1, and it becomes readily apparent that the larger balls lose substantially more weight in a given length of time. Fig. 2 is a graphic record of the average percentage weight loss for each size group in mill No. 1, illustrating that the smaller balls definitely lose a greater percentage of their original weight in a given length of time. It was, therefore, decided to convert the actual weights of the test balls to diameter and follow the diameter losses periodically to see if the wear rates

Jan 1, 1951

By C. R. Fulton

The idea of making permanent magnets by sintering is not a new one, but until the introduction of the iron-nickel-aluminum permanent-magnet alloys there was little need for such a process. Permanent-magnet alloys in use up to the time of this development could be forged and machined to the exact size or shape required without too much difficulty. These new Fe-Ni-A1 alloys, which have become known as Alnico in this country, soon became very popular because of their superior magnetic properties, but when they were made by casting they did have some disadvantages when compared with the older type of permanent-magnet steels. Among these disadvantages were the following: 1. It was almost essential that they be cast to size, since they could not be readily forged or machined. The material could be ground but this was quite expensive, particularly for small magnets in large quantities. 2. The material had a large grain size and was mechanically weak. 3. Close tolerances could not be held and on small magnets this meant grinding almost the entire magnet. Because of the brittle nature of the material, there was considerable loss due to chipping and cracking during these grinding operations. 4. Because of its high aluminum content, the molten alloy had a high surface tension. It was difficult to prevent loss of aluminum by oxidation during the melting operation. In view of these difficulties it is not hard to understand why a process for sintering alnico was developed, or why sintered alnico has come into such widespread use in recent years. It might be well to qualify this by saying that it has come into widespread use for small magnets weighing 2 oz. and less, of the type shown on Fig. I. In this size range, sintered alnico has been able to compete in price with cast alnico. Magnets larger in size, of the type shown on Fig. 2, can be made but they do not compare favorably in price with the cast material. An idea of the range of sizes that have been produced is given by Fig. 3, which shows a small magnet weighing 0.006 oz. and a large magnet with a steel insert weighing 4 lb., both made from sintered alnico. Magnets weighing more than 2 oz., however, should not be made from sintered

Jan 1, 1945

By W. T. Lundy

THE forms in which sulphur is commonly found-native sulphur, sulphides of many metals and sulphates-are widely distributed throughout the world. The two first mentioned are the principal sources of sulphur. Substantial amounts of sulphur in some form are recovered from gases from industrial plants and from gases from smelters treating other minerals. In recent years, plants have been installed in the United States to recover sulphur in elemental form from sour gases."' The amount of sulphur so produced is small at the present time but undoubtedly will increase in the future. The recovery of sulphur from gases is not covered in this chapter, which is confined to: (1) native sulphur deposits of Texas and Louisiana; (2) those of Italy; (3) other scattered deposits of native sulphur; and (4) pyrites deposits found in many countries of the world.30 Sulphur, a nonmetallic element, occurs normally in well developed bipyramidal or tabular crystals of the orthorhombic system, as well as in stalactitic and earthy masses. The mineral has a distinctive yellow color, which may be dark and discolored by impurities; the streak is white; the luster is resinous; and the fracture is conchoidal to uneven. Sulphur is translucent to opaque; has a hardness of 1.5 to 2.5, a specific gravity of 2.05, and an atomic weight of 32.06.16 The molecular weight of the solid is expressed by the symbol SS and that of the liquid and vapor ranges from S2 to S8, depending on the temperature. Sulphur melts at a temperature between 2340 and 248°F, depending on its crystalline state, to a liquid of dark amber color, the boiling point of which is 832°F. The viscosity near the melting point is about that of water and increases to 50,000 times that of water at a temperature of 380°F, subsequently falling rapidly to a low figure at the boiling point. Crystallization changes slowly from rhombic to monoclinic above 205 °F and in cooling the transformation is reversed. The mineral is a very poor conductor of heat and electricity; it is insoluble in water and nearly all acids and is soluble in cold carbon bisulphide and carbon tetrachloride. It ignites in air at a temperature of 478°F, burning with a distinctive blue flame with evolution of sulphur dioxide.47

Jan 1, 1949

By L. G. Austin, R. R. Klimpel

This article demonstrates that the Gilvarry and Klimpel-Austin equations for the random fracture of solids are incorrect by deriving intuitively correct expressions for simple cases and showing that the foregoing equations do not reduce to right answers. It is the purpose of this article to point out serious errors in some existing treatments of the random fracture of solids. Gilvarry ' gives the equation where B(y,x) is the cumulative fraction by weight of particles which fall below size y when particles of size x are broken. The constants i, j, k contain shape factors and densities of flaws leading to propagating fracture surfaces. The authors believe this equation to be incorrect. Klimpel and usttin' give where r~ is the number of fracture planes originating from edge flaws (per L where L is the edge length of the original particle), rs is the number of fracture planes originating from flaws on the particle surface (per S where S is the surface of the original particle) and rv is the number of fracture planes originating from flaws within the particle volume. This equation is also incorrect. The failures of these equations will be demonstrated by deriving intuitively correct expressions for simple cases and showing that the Eqs. 1 and 2 do not reduce to the correct answer. In this process, the flaws in statistical reasoning inherent in the derivations of Eqs. 1 and 2 become apparent. THE KLIMPEL-AUSTIN EQUATION Eq. 2 was derived by considering a set number of fracture planes occurring spatially at random within a given particle. This case will be treated here in its simplest form: a line with 1, 2, 3, etc., fractures occurring at random. This is illustrated in Fig. 1, with the original length of the line as Vo. The breakage of a long, thin, brittle fiber is a corresponding physical case, with the volume of a fragment proportional to its length. Assuming independence of the occurrence of the fractures, the probability of any one fracture occurring in length dV is dV/V0. The probability of the first fracture occurring at a length V to V + dV is dV/Vo. For the case of only one fracture per particle, formation of a number-size distribution of the left-

Jan 1, 1969

By A. M. Kivari

OPERATIONS at the cement plant of the Permanente Corporation, in the hills about 45 miles south of San Francisco and 12 miles west of San Jose, are interesting to the members because of the adoption of modern hydrometallurgical methods for handling and beneficiating raw materials. Closed-circuit grinding, classification, hydro-separation, flotation, agitation, and thickening are familiar terms at this cement plant. These methods make it possible to process refractory limestone into suitable materials for the manufacture of modern cements. Construction of the plant, having originally a design capacity of 7000 bbl. of cement per day, was started in June 1939, and the first clinker was ground on the following Christmas Day. At present the capacity is about 12,000 bbl. of finished cement per 24 hr., most of the production being low-heat cement.† About 3130 tons of limestone, 620 tons 0f clay and 100 tons of gypsum are required daily for this output. Occasionally iron oxide is added to the clay to obtain the desired composition. This, together with the gypsum, is purchased from outside sources. Up to the present time, the corporation has produced low-heat, normal, moderate heat, moderate-sulphate-resisting, high-early-strength, oil-well, modified-oil-well, and plastic cements. Most of the present production is for Shasta Dam, near Redding, Calif., the total demand being 5,800,000 bbl, of cement. Following are some of the cement requirements of the Shasta Dam specifications: [PERCENT Chemical composition: Loss in ignition2.25 Insoluble residue0.75 SO32.25 MgO5.00 Uncombined lime in clinker (CaO)1 .25 Percentage of iron oxide to alumina ratio1.5 Compound composition: Tricalcium silicate (3CaO.Si02)Not more than 3,5 Dicalcium silicate (2CaO.Si02)Not less than 40 and not more than 65 Tricalcium aluminate (3CaO.Al2O7)Not more than 7 Tetracalcium aluminoferrite (4CaO.A12O3.Fe203) Not more than 0 Fineness:] The average specific surface in the bin sampled shall be not less than 1800 sq. cm. per gram and no individual sample less than 1600 sq. centimeters. Compressive strength: The average compressive strength-in pounds per square inch of three mortar cubes composed of one part cement and 2.75 parts fine testing sand, by weight, shall be equal to or greater than the following:

Jan 1, 1941

By Hans W. Schreiber, David W. Neuhaus

INTRODUCTION The Sunshine Mining Company's 16-to-1 silver deposit and mine project are located 384 kilometers (240 miles) southeast of Reno and 360 kilometers (225 miles northwest of Las Vegas, near Silver Peak in Esmeralda County, Nevada, at an elevation of about 2,300 meters (7,000 feet). The deposit was being developed, in 1980, with an anticipated mining and milling rate of 150,000 tons per year (500 tons per day). Mining is by underground, blast-hole open stoping with rubber-tire haul-age out of the mine to a straight cyanide plant about 5.5 kilometers (3.5 miles) from the mine. The product is a gold-silver dore which may be further refined at Sunshine's new refinery in Kellogg, Idaho. The cash required for investment was obtained through the sale of $25 million worth of 6 l/2h silver-indexed bonds. Some $15.0 million were directed toward development of the 16-to-1 Mine. These bonds, which were underwritten by Drexel Burnham Lambert of Chicago in April of 1980, are redeemable on or after April 15, 1985 or payable at maturity on April 15, 1995 at the greater of either $1,000 or the market price of 50 ounces of silver. Behre Dolbear acknowledges the kindness of the Sunshine Mining Company (Sunshine) for allowing the presentation of the subject material for this Case Study. APPLICABILITY AS CASE STUDY Reasons for Choosing 16-to-1 The reasons for choosing the 16-to-1 Mine as a case study follow: 1. The project is simple and compact. 2. The mine is small -- thus relevant to other contemplated precious metal operaions in the western states. 3. The areas of risk are readily identifiable. 4. A change to project financing was under consideration. 5. A substantial decline in the price of silver was experienced during development. 6. Behre Dolbear undertook one of the first feasibility studies of The 16-to-1 and thus has some familiarity with the project. Historical Summary The following history serves as a setting: 1. Late 1920s -- minor "production"(?) via shallow pitting. 2. Mid-1930s -- neighboring Nivlok Mine successfully put into production. 3. Late 1950s (?) -- Callahan Mining Company acquired rights and drilled -- results inconclusive; Callahan turned property back to Arthur Baker, who had originally interested Callahan in 16-to-1 on the basis of its similarity with Nivlok Mine.

Jan 1, 1985

By I. H. Pratt

The results of a study on the preparation of thin-film capacitor structures are discussed. The dietectric source material was quartz which was sputtered and deposited onto aluminum electrodes and counter-electroded to complete the metal-oxide-metal structures. This configuration was utilized to evaluate the dielectric, the device characteristics, and related process parameters. The effect of gas sputtering pressure, magnetic field strength, source-to-substrate distance, and power density on the rate of deposition is shown. Increased film thickness uniformity over a 3 by 3 in. area by optimum substrate positioning is indicated. Dielectric constant, dissipation factor, dielectric breakdown strength, insulation resistance, heat treatment, capacitance, and dissipation over the range 400 Hz to 5 MHz are reported. In the fabrication of silicon-integrated circuits, silicon dioxide has found use as a material suitable as a diffusion mask, for surface passivation of the silicon, and for protection of conductive films used for interconnections. Its use as a dielectric for thin-film capacitors in film hybrid circuits has been limited, to a degree, for lack of a compatible processing technique and because of its relatively low dielectric constant. With the recent advent of practical metal-oxide-semiconductor (MOS) field effect devices, the material is now being used to insulate the gate electrode from the conducting channel in the silicon. In this latter application, more stringent requirements have been imposed on .the oxide. A comprehensive resume of the use of silicon dioxide in integrated silicon device technology has been compiled including oxide film and bulk properties, method of oxide formations, and their applications.' A relatively new process to deposit SiO, and other dieIectrics is by rf sputtering, and the purpose of this paper is to describe the behavior of capacitors fabricated with a dielectric which has been sputtered from a quartz target and to indicate the relative effect of several of the process parameters on the film deposition. Work on rf sputtering of SiO2 and other dielectrics has been reported utilizing a triode type of sputtering system as described herein or a diode self-sustained glow discharge system. 2-8 SPUTTERING The process occurs during an electrical discharge in a gas plasma which provides the ions for acceleration to the target to produce the desired sputtering. The necessary plasma can be generated by a dc glow discharge through application of a high potential between two electrodes at approximately 2 to 10 x 10-2

Jan 1, 1969

By K. H. G. Ashbee, J. W. Heavens

One consequence of the distribution in orientation of Bragg diffracting planes in an elastically bent foil is that simultaneous diffraction occurs from ±g pairs, where g is the reciprocal lattice vector to a diffracting plane. If such Bragg contour pairs are indexed, then the variation in orientation with respect to the incident electron beam is known. This note describes a construction by means of which Bragg contour pairs may be indexed by inspection. Referring to Fig. 1, the Ewald sphere radius is l/h, where is the wavelength of the electron beam, and the half spacing of first-order reciprocal lattice planes is l/d, where d is the corresponding spacing in direct space. The angle subtended by the zero and first-order planes at the center of the Ewald sphere is a = sin-' Thus, to represent a pair of first-order Bragg contours on a stereographic projection, measure ±a from, and along the normal to, the zero-order plane. The traces of the required Bragg contours pass through these points and parallel to the zero-order trace. In practice, it is desirable to enlarge a stereographic projection of the zero-order planes before making the construction. As an example, a stereographic projection of first-order Bragg contours up to line 27 for an fcc crystal is given in Fig. 2; if required, higher-order contours can easily be added. Fig. 2 is, of course, a map of first-order Brillouin zone boundaries. One use of this construction is the measurement of large elastic fields in electron microscope specimens. Fig. 3(a) shows a pattern of Bragg contour pairs due to lattice distortions near a large precipitate. This particular example is of a T-phase precipitate in Hidu-minium 54 (A1 + 6 wt pct Cu, 0.5 wt pct Mn). Foil buckling is produced by annealing during observation and may be evidence for evaporation from the precipitate.' Comparing Figs. 2 and 3(0), it is evident that the axis of high symmetry in Fig. 3(a) is [lll]. The strain in a bent foil is approxinlately t/2r, where / is the foil thickness and ? the radius to which the foil is bent. From the projections of grain boundaries and of helical dislocations, it was estimated that ( - 3000A, and values for ? were obtained from the

Jan 1, 1968

By Louis A. Carapella, Ralph Hultgren

WHEN F. Heusler1 found in 1898 that certain alloys containing only copper, manganese, and tin were ferromagnetic, the discovery excited a great deal of interest and led to numerous investigations. It was early found that tin could be replaced by aluminum, arsenic, antimony, bismuth, or boron without destroying the ferromagnetic nature of the alloys.2 Copper may also be replaced by silver.3 All these alloys have come to be known as "Heusler alloys." The aluminum alloys apparently were the most magnetic and have been most extensively investigated. However, no agreement has yet been reached as to the source of the ferromagnetism arising from these nonferromagnetic elements. Absence of reliable quantitative data makes speculation hazardous. The value of much of the earlier work was vitiated by lack of necessary precautions against contamination, and by lack of close control of heat-treatment. It was only recently established that in aluminum Heusler alloys" the ferromagnetism arose from a single phase, an ordered body-centered-cubic structure. With modern methods of preparation, heat-treatment, and X-ray examination, it is possible to prepare these alloys without contamination, to heat-treat them intelligently, and to determine what phase or phases are present in the finished sample. In the present investigation, a series of pure alloys in the comparatively neglected copper-manganese-tin system have been prepared, which consist of a single, body-centered-cubic structure (the beta phase) and whose compositions vary within wide limits. The magnetic saturation values of these single-phase alloys have been quantitatively determined, so that considerable data on the effect of composition on the ferromagnetism have been made available. In the course of the investigation some information on the extent of the stability of the beta phase and the nature of phases in adjacent regions of the ternary diagram has been accumulated. Anomalies in earlier data have been explained, and alloys have been prepared that are much more strongly magnetic than any previous Heusler alloys. PREVIOUS WORK In the original work of F. Heusler1 and coworkers,2 a maximum magnetic saturation value of I = 107 was found at the composition Cu6Mn3Sn, while a value for Cu2MnA1 of I = 443 was early measured. Ross and Grays found a second maximum at the composition Cu2MnSn, which was much more magnetic than Heusler's original alloy. F. Heusler6 then reinvestigated the system, confirmed their results,

Jan 1, 1941

By F. A. Forward, A. H. Ross, J. Halpern

IN treating carnotite ores by carbonate leaching it is often necessary to subject the ore to a prior roast. Among the advantages that may result from roasting are: 1) improvement in settling and filtering characteristics of the ore; 2) destruction of carbonaceous impurities that would otherwise contaminate the leach solution and consume carbonate reagent; and 3) substantial increase in extraction of vanadium, which is usually low when the un-roasted ore is leached. Recovery of vanadium may be an important factor in processing carnotite ores, and the fact that vanadium is usually recovered in good yield by acid leaching has often been an economic advantage over results obtained with carbonate leaching. It has been found that response of an ore to carbonate leaching, following roasting, depends primarily on its composition and on the conditions of the prior roast treatment, particularly with regard to the roasting temperature, the atmosphere maintained above the charge during roasting and cooling, and the presence of certain reagents. These factors, especially the last, virtually determine the extractions of uranium and vanadium attainable by carbonate leaching, as well as the reagent consumption on leaching, whereas adjustment of the leaching conditions has only a limited influence. These variables were examined systematically to elucidate roasting and carbonate leaching of carnotite ores and to establish a treatment yielding high recoveries of both uranium and vanadium. Tests were conducted on samples of four different Colorado Plateau ores, described in Table I. Roasting Procedure: The roasting tests were conducted in an electrically heated furnace in which the temperature was controlled to +15oC. The ore (usually a 500-g charge) was ground to —100 mesh, mixed with the desired reagent, and spread in a silica tray to a bed depth of about 1/2 in. During the roast the charge was rabbled at intervals of 15 min. To provide free access of air the furnace was usually ventilated; however, in a few experiments a controlled atmosphere such as carbon dioxide or hydrogen was maintained above the charge. Leaching Procedure: The pulp, generally comprising 500 g of ore and a 2000-cc solution containing 80 g per liter of Na2CO3 and 20 g per liter of NaHCO3, was agitated in an autoclave at 120°C, under 30 psi O2. Samples were withdrawn periodically, and the solution and ore residue were analyzed. Under the conditions employed, maximum attainable extractions were generally achieved in 4

Jan 1, 1958