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By J. B. Cheatham, J. W. McEver

A laboratory investigation of the behavior of casing subjected to salt loading indicates that it is not economically feasible to design casing for the most severe situations of nonuniform loading. When the annulus is completely filled with cement, casing is subjected to a nearly uniform loading approximately equal to the overburden pressure, and, although the modes of failure may be different, the design of casing to withstand uniform salt pressure can be computed on the same basis as the design of casing to withstand fluid pressure. Failure of casing by nonuniform loading in inadequately cemented washed-out salt sections should be considered a cementing problem rather than a casing design problem. INTRODUCTION Casing failures in salt zones have created an interest in understanding the behavior of casing subjected to salt loading. The designer must know the magnitudes and types of loading to be expected from salt flow and he must be able to calculate the reaction of the casing to these loads. In the laboratory study reported in this paper, short-time experimental measurements of the load required to force steel cylinders into rock salt are used as a basis for computing the salt loading on casing. These results must be considered to be qualitative only since rock salt behaves differently under down-hole and atmospheric conditions and also may vary in strength at different locations. The beneficial effects of (1) cement around casing, (2) a liner cemented inside of casing, and (3) fluid pressure inside of casing in resisting casing failure are considered. ROCK SALT BEHAVIOR UNDER STRESS The effects of such factors as overburden loading, internal fluid pressure, and temperature on the flow of salt around cavities have been studied extensively at The U. of Texas. Brown, et al.1 have concluded that an opening in rock salt can reach a stable equilibrium if the formation stress is less than 3,000 psi and the temperature is less than 300°F. At higher temperatures and pressures an opening in salt can close completely. These results indicate that calculations based upon elastic and plastic equilibrium for an open hole in salt should be applied only at depths less than 3,000 ft. In most oil wells the tem- perature will be less than 300F in the salt sections, therefore no appreciable temperature effects are anticipated. Serata and Gloyna2 have reported an investigation of the structural stability of salt. .They assume that the major principal stress is due to the overburden. Other stresses can be superimposed if additional lateral pressures are known to be acting in a particular region. In the present analysis an isotropic state of stress is assumed to exist in the salt before the hole is drilled, since salt regions are generally at rest. This assumption is partially verified from formation breakdown pressure data taken during squeeze-cementing operations in salt. Experimental measurements of the elastic properties of rock salt indicate a value of 150,000 psi for Young's modulus and a value of approximately 0.5 for Poisson's ratio. A value of % for Poison's ratio with finite Young's modulus would indicate that the material was incompressible. Values ranging from 2,300 to 5,000 psi have been reporteda for the unconfined compressive strength of salt. These variations may be due to differences in the properties of the salt from different locations or at least partially to differences in testing techniques. Salt is very ductile, even under relatively low confining pressures. For example, in triaxial tests reported by Handin3 strains in excess of 20 to 30 per cent were obtained without fracture. When casing is cemented in a hole through a salt section, the casing must withstand a load from the formation if plastic flow of the salt is prevented. To determine the forces which salt can impose on casing, circular steel rods were forced into Hockley rocksalt with the longitudinal axis of the rods parallel to the surface of the salt. The force required to embed rods 0.2 to I in. in diameter and 1/2 to 1 in. long to a depth equal to the radius of the rods was found to be F/DL =28,700 psi (± 3,700 psi) , .... (1) where D is the diameter, and L is the length of the rod. CASING STRESSES Since an open borehole through salt at depths greater than 3,000 ft will tend to close, cemented casing which prevents closure of the hole will be subjected to a pressure approximately equal to the horizontal formation stress after a sufficiently long time. As a first approximation the horizontal stress can be assumed to be equal to the overburden pressure. This is in agreement with the suggestion by Texter4 that an adequate cement job can prevent plastic flow of salt and result in a pressure on the casing approximately equal to the overburden pressure. He also advocated drilling with fully saturated salt mud

Jan 1, 1965

By I. G. Bowen

The pumping of abrasive and sometimes corrosive slurries is normally carried out at modest heads (say 100 ft) with specially designed centrifugal pumps. When heads become higher than this, two or more pumps are used in series but ultimately the system requires staffed pumps with consequent increase of costs. The only other type of pump suitable for high heads is the Ram pump but this is notoriously subject to wear. The paper describes a novel application of the so-called "lock hopper" principle to continuous pumping of slurries. The pump itself is never in contact with the abrasive slurry nor is it subject to head or capacity limitation. It works by displacing slurry with the clear fluid component of the slurry (in most cases water) through cylindrical vessels fitted with plug valves to control the discharge and filling operations. Two such vessels are used and the scheme is completed with a liquid clarifier which allows the pipe flow to be maintained continuously. The paper describes experience on the prototype unit used to discharge tailings from a coal washery in Scotland. A tentative evaluation is also made of the economics of this pump against conventional equipment.

Jan 1, 1965

By W. B. Gogarty

The reported decreases in water mobility do not seem unusual in view of non-Newtonian fluid properties. Shear stress vs shear rate diagrams have been reported for other solutions of water-soluble polymers. Some of these polymers are similar to the type mentioned by the author. Generally, the shear stress-shear rate is a non-linear function for these solutions. Data for plotting apparent viscosity vs shear rate can be obtained from this function. Apparent viscosity is defined as the ratio of shear stress to shear rate at a given shear rate. When plotted, the apparent viscosity decreases with increasing shear rate. This behavior is typical of a pseudoplastic fluid. For some water-soluble polymer solutions, the apparent viscosity decreases more than 50 times while the shear rate increases 1,000 times. Thus, viscosity of a pseudoplastic fluid only has meaning at a specified shear rate. Results of Fig. 1 could be explained in these terms. Viscosities measured in the Ostwald viscometer represent values at a given shear rate. Some average shear rate is affecting the polymer solutions while flowing through the core. This average value fixes the apparent viscosity as long as the flow rate remains constant. Viscosities measured by the two methods will be equal if shear rates are the same. The results indicate that shear rate in the core is lower (higher apparent viscosity) than in the viscometer. In the paper by Johnson, Bossler and Naumann, the relative permeability is independent of viscosity ratio. Thus, the relative permeability with respect to water flow at residual oil should be independent of the flowing phase viscosity. Polymer solutions will appear as Newtonian fluids The discussion emphasizes the nature of the "resistance factor effect" as discussed in the paper. Repeated anomalies arising in hundreds of experiments led us to the conclusion that non-Newtonian flow is not the only factor. Several of the key anomalies are as follows: 1. Measured viscosities over a range of shear rates from <1 sec-&apos; to 1,000 sec-&apos; do not account for but a minor fraction of the R observed in cores when compared in similar shear-rate ranges. 2. The slope of R vs flow rates in cores is always different from that expected from viscometer shear-rate measurements as shown in Fig. 2. in a core, the level of viscosity being fixed at a given flow rate. With these conditions, the definition of resistance factor R by Eq. 2 is simplified to Since , is constant with rate, R becomes a measure of the apparent viscosity in a core at a given flow rate. Variation in flow rate could easily account for the changes of R shown in Fig. 5. Also, this points to the fallacy of assuming R to be a unique parameter. The constant resistance factors at different flooding velocities appear to be in disagreement with the above discussion. The author furnishes Fig. 2 to support his arguments. As shown, the resistance factors remained substantially constant in the two cores over a considerable range of flooding velocities. However, in the 73-md core, the factor increases at lower rates. This behavior agrees with known characteristics of some pseudoplastic material. These materials act both as Newtonian and as non-Newtonian fluids in different regions of shear rate. Some exhibit first Newtonian, then non-Newtonian, finally, Newtonian character. Others are first non-Newtonian and then Newtonian. This latter type would explain the results with the 73-md core. The Fann-instrument results are not significant since shear rates in the core may be much different than with the viscometer. The higher resistance factor at high rates in the 150-md core is more difficult to explain. The greater resistance at increased flow rates could be attributed to what might be termed temporary bridging. As envisioned, changes in polymer configuration occur at the higher energy associated with the increased flow rate. These changes could cause less effective passage of polymer through the core. Correspondingly, increases in pressure drop will occur. These will be interpreted as higher resistance factors. 3. Most polymer solutions are non-Newtonian and many are more shear-rate sensitive than the polymers in question, yet only a very few polymers demonstrate useful R values. Gogarty&apos;s assumption that viscosities in cores and vis-cometers will be the same if measured at the same shear rate is only valid if non-Newtonian rheology is the only parameter. The experimental evidence does not validate this assumption. The anomalies observed in the equilibrium displacement experiment shown in Fig. 5 are not explained on the basis of varying flow rates since the rates were held constant. M

Jan 1, 1965

By R. R. Joseph, K. A. Gschneidner

The solid solubility of magnesium in the close-packed modifications of lanthanum, cerium, praseodymium, neodymium, gadolinium, dysprosium, and lutetium was determined from approximately 250°C to the eutectoid temperature by the X-ray parametric technique. The maximum solubility at the eutectoid temperature was found to be 9.4 at. pet in La, 8.2 in Ce, 9.2 in Pr, 8.2 in Nd, 14.1 in Gd, 13.5 in Dy, and 11.5 in Lu. The solubility when compared at a homologous temperature was found to increase in a smooth manner with decreasing size factor from lanthanum to lutetium. It was found that the apparent atomic radius of magnesium when dissolved in the lanthanide solvent was constant and could be accounted for by consideration of several models dealing with departures from Vegard&apos;s law. The eutectoid temperatures for the lanthanide-rich La-Mg, Ce-Mg, and Nd-Mg systems were found to be 544", 505°, and 551°c, respectively. A study of the solid solubility of magnesium in the lanthanide metals was initiated because the valency and electron egativity difference are essentially constant and favorable for solid-solution formation, and thus one could examine the effect of size on terminal solid solutions. The size factors based on metal radii range from 14.6 pet for lanthanum to 7.5 pet for lutetium. Since the electronegativity difference is small, 0.06 unit or less, application of the Hume-~othery&apos; and Darken and Gurry2 criteria for solid-solution formation indicates that the solubility of magnesium would be expected to be small for lanthanum (between 5 and 10 at. pet) and to increase as we proceed along the lanthanide series. A search of the literature revealed no data on the solubility of magnesium in the lanthanide metals except for the solubility of magnesium in cerium at 450oCA typical phase diagram for the lanthanide-rich end of the lanthanide-magnesium phase diagram is shown in Fig. 1. EXPERIMENTAL PROCEDURES Preparation of Alloys. The lanthanide metals used in the preparation of alloys for this investigation were prepared from the corresponding fluoride by metallothermic reduction techniques previously described by Daane.4 The chemical analyses of the metals used are listed in Table I.

Jan 1, 1965

By C. O. Hawk

A PART of the Bureau of Mines effort to improve the conversion of coal to liquid fuels, batch autoclave tests were made on the hydrogenation of bituminous coal by a dry method, which featured charging the autoclave with dry ingredients only-coal, catalyst, and hydrogen. This innovation, which omitted the liquid vehicle used in earlier work, limited the products to those made from the coal charged. The effects of the common process variables (catalyst, hydrogen pressure, temperature, and residence time) were studied. Tin catalysts showed the highest activity in the widest variety of forms and were the easiest to disperse; dry mixing in the autoclave during the heating-up period usually sufficed. Ammonium molybdate, on the other hand, was inactive when dry mixed, but it compared favorably with the best catalysts known when applied by impregnating the coal with a solution of a molybdenum compound. As a group, metal naphthenates were the most effective; in fact, molybdenum naphthenate was the most active catalyst the Bureau tests disclosed. One-hundredth of a percent of molybdenum in this form (calculated as the metal in weight-percent of maf coal) induced 90-percent conversion of coal. However, because of their high cost, naphthenates have as yet only technical significance in coal hydrogenation. Long residence time and high reaction temperatures tend to increase the amount of thermal decomposition products formed (light hydrocarbon gases and/or char). High hydrogen pressure favors the production of liquids.

Jan 1, 1965

By F. W. Osterwald, C. R. Dunrud

A continuously recording seismic network was constructed in 1962 by the U.S. Geological Survey to locate epicenters and record incidence of bumps (bounces, rock bursts) that occur in the bituminous coal mines of the Book Cliffs coal field near Sunny-side, Utah. The coal is mined because of its value as coking coal, although these bumps may be a hazard to life and property. Daily records of tremors caused by bumps for 1 3/4 years indicate that a seasonal pattern, as well as a daily pattern, exists for the number of bumps that occur in a given period. Maxima occur in May and June and November and December. Marked increases at 5-day to 9-day intervals are superimposed on these seasonal maxima. The largest bumps commonly occur during seasonal maxima when the rate of occurrence suddenly decreases and the amplitude of the individual bumps increases. Knowledge of this pattern may lead to prediction of general locations and periods of increased hazard from bumps. Experience to date has shown that prediction of precise times and locations of hazardous bumps is not possible, and may never be; primarily because even a small bump can be a hazard to life and property. Some bumps or bump sequences are actually composites, consisting or two or more discrete bumps a few tenths of a second to a few seconds apart. Violent and spontaneous releases of coal and rock from faces, ribs and roofs of mines (termed bumps or bounces by miners) are a common hazard to life and property in the coal mines located in the Book Cliffs near Sunnyside, Utah (Fig. 1). These bumps

Jan 1, 1965

By K. C. Dean

This report is the first of a series concerned with processes for producing magnesium. These reports will evaluate metallothermic, carbothermic , and electrolytic production methods, and will furnish a cost basis for comparing the processes. Areas deemed most promising for future research will be delineated for each procedure. This report presents briefly the history of the metallothermic process, and describes the operations of the Defense Plant Corp. (DPC) plants that employed the process. A hypothetical plant designed to produce 12,000 tons of magnesium per year, using ferrosilicon as a reductant, is described, and raw materials, energy, and major equipment requirements are estimated. Several process modifications are suggested for future research.

Jan 1, 1965

By A. T. Harris

Ground quartzite, known in the industry as amorphous silica, is produced from a quartzite deposit near Honey Brook, Pa., by George F. Pettinos, Inc., of Bala-Cynwyd, Pa. The quartzite is mined by the open pit method and processed in a mill at the mine. The operation regularly produces five standard grades of sand and one grade of crushed stone; however, the company accepts special orders and will produce material to meet the customer&apos;s specifications. Beneficiation (chiefly crushing and screening) is controlled by laboratory screen tests on samples taken during preparation of the sand. The chief uses of the sand are for foundry operations, furnace lining, concrete aggregate, and Other specialized uses. The quartzite in this deposit is of uniform composition and does not require control by chemical analysis. However, for special purposes, analysis will be furnished.

Jan 1, 1965

By P. M. Kelly

TWO analytical methods for calculating the positions of matrix and twin reflections on electron-diffraction patterns of a twinned cubic crystal have recently been published.1,2 Meieran and Richman1 considered the case of twinning on (1 12) in a bcc structure, while a more general treatment, capable of analyzing twinning on any plane in a cubic crystal, was developed by Johari and Thomas.2 The latter authors applied their general rotation matrix to both (111) twinning in face-centered crystals and {112} twinning in body-centered crystals and they derived separate expressions for these two cases. This separate treatment masks the fact that in a holosymmetric cubic crystal a (111) twin is crys-tallographically equivalent to a {112} twin.3 This is analogous to the crystallographic equivalence of rotation and reflection twins in centrosymmetric crys tals. A particularly simple example of this equivalence occurs when the two twin planes are perpendicular to each other—for example (111) and (112). Then, if twinning on (111) moves a point P to a new position P1, and twinning on (112) moves P to P2, P1 and P2 will be related to each other by a 180-deg rotation about [110]— the direction normal to both (111) and (112). Since there are diad axis axis along (110) direction in a holosymmetric cubic crys tal the two positions P1 and P2 must be crystallo-graphically equivalent. In other words if a particular pole (hk l) is in a position P1 after twinning on (Ill), then after twinning on (112) a pole of the type {hkl}—but not the particular pole (hk1)—will also be in the position P1. As a result, when only the general (as opposed to the particular) indices of poles after twinning are required, twinning on (111) gives the same results as twinning on (112). To convert the results for a (111) twin to those applicable to a (112) twin, when the particular (as opposed to the general) indices of poles after twinning are required, all that is necessary is to multiply the indices of the twin poles by the matrix for 180-deg rotation about [lie], i.e., The analytical methods suffer the disadvantage that a new set of calculations must be performed for each different diffraction pattern or, as is done in the Meieran and Richman treatment,1 a lengthy list of the location of the twin spots in reciprocal space must be prepared. All the tedious computation involved in these analytical approaches can be avoided by simply plotting, on tracing paper, a stereographic projection of a crystal twinned on say (112). By superimposing this twin stereogram on a standard (001) projection (preferably with the points and indices in a different color from those on the twin stereogram) the relative positions of both matrix and twin reflections can be determined by inspection. Alternatively, a composite projection can be

Jan 1, 1965

By James A. Deane

Strip mine reclamation Fs the process of restoring the land affected by the mining process to its most productive use. This can be timber production, pasture, crop land, wildlife and/or recreational use. The mining companies must determine, through the advice of their technicians, what the most advantageous use of the land will be. If the Company does not own the surface, the owner or owners must be contacted to determine their desires as to how the land should be reclaimed. Many times, in making the plans to restore an area with vegetative cover, the watershed and the quality of the water in the area is overlooked. The water itself must be an integral part of the reclamation plan. Many lakes and/or pits can be created with proper planning. In areas in the Midwest, where lakes are a scarcity, these strip mine lakes can become storage reservoirs for large amounts of water, They can help control runoff and low flow augmentation. The strip mining operation will affect the watershed regardless of whether a reclamation plan in made or not. It is up to the reclamation technician to see that the plan benefits the watershed instead of affecting it adversely. This can be done during the operation by intercepting the water before Pt enters the active pit. Diversion ditches above the highwall will handle the runoff water from the watershed. Water that does gain entry into the pit should be removed as quickly as possible. If the rules and regulations adopted by the Ohio River Valley Sanitation Commission in Resolution 5-60 are followed, water encountered during the operation can be handled with little or no adverse effect to the receiving watershed.

Jan 1, 1965

By Donald E. Grimes

In conjunction with Inland Steel&apos;s development of lead-bearing steels possessing improved machin-ability because of tellurium and/or selenium additions, it was decided to determine liquidus and solidus temperatures in the Pb-PbTe-PbSe sub-ternary system. With the exception of alloys in the PbTe-PbSe system, it is believed that no previous study of this subternary has been performed. Thermal analysis was employed in a general survey of the subternary. In addition to PbTe, PbSe, and pure lead, ten ternary compositions were selected at intervals of ten at. pct. Sixty-gram alloys were prepared by sealing an appropriate mixture of the elements in quartz crucibles with a central thermocouple-well under a vacuum of less than 10 p. All three elements were 99.999+ pct pure with only trace impurities detected by spectroscopic examination. After the alloys had been heated at least 20°C above the liquidus in a Kanthal furnace, cooling and heating curves were obtained. Two or more cooling curves were employed both for the determination of each alloy liquidus and for the solidus of those al- loys containing greater than 50 at. pct Pb. Cooling rates were 0.5° to 3.5°C per min during the 5 min immediately prior to the start or end of solidification. For those ternary alloys containing 50 at. pct Pb, the solidus was determined from heating curves. Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple which was calibrated in the same apparatus against the freezing points of zinc (A. D. MacKay—99.999 pct), antimony (A. D. MacKay-99.999 pct), and copper (ASARCO—99.999+ pct) both before and after the experimentation. The only interruptions in the continuous strip-chart recording of the temperature occurred for brief periods at significant points of interest when direct readings were made with a Rubicon Type B potentiometer sensitive to * 1 µv. The average liquidus and solidus temperatures obtained in this investigation are listed in Table I together with probable errors based on the accuracy of the thermocouple calibration and the reproduci-bility of the data. No chemical analyses of the alloys were performed because the synthetic or as-charged compositions were felt to be reliable. The melting points obtained for PbTe (924.7° ± 0.7°C) and PbSe (1084.0° ± 0.6°C) compare favorably with recent findings of other investigators.&apos;-&apos; As indicated in Table I, both the liquidus and solidus temperatures increase as selenium replaces tellurium for a constant atomic percent lead. As a result, the ternary liquidus and solidus temperatures for a given percent lead lie between the corresponding binary temperatures published in the literature. It should be noted that those ternary alloys containing 50 at. pct Pb exhibit a relatively narrow liquid-plus-solid region (<80°C) when compared with alloys containing greater than 50 at. pct Pb. Alloys with 60, 70, or 80 at. pct Pb not only have a much wider liquid-plus-solid region (>500°C) but also exhibit considerably lower and approximately constant solidus temperatures which thus form a virtually isothermal solidus "plane" slightly below the melting point of pure lead (327.3°C). For these alloys

Jan 1, 1965

By J S. Kermeen

This paper deals with drilling and blasting techniques at the Phoenix mine, near Grand F1nks, B.C., which is now operated by The Granby Mining Company Ltd. The difficulties of open-pit mining through former underground workings are unique to this operation. Rock types are related to drilling conditions, and the methods used, or contemplated, to overcome the several difficulties are outlined. The equipment used is also mentioned. Finally, blasting techniques and costs are reviewed. Introduction T HE Granby Mining Company operates on open-pit copper mine and concentrator at the site of the original Phoenix mine, near Grand Forks in south-central British Columbia. The pit is a side-hill cut measuring approximately 1,000 by 2,000 ft., and covering a vertical range of from 4,550 to 4,950 feet above sea level. The mill is currently operating at 1,900 tons per day. A 4.5 to 1.0 waste to ore ratio necessitates the removal of some 15,000 tons of ore and waste per working day. Mining conditions at Phoenix are extraordinary in that all the ore zones currently being

Jan 1, 1965

By B. B. L. Seth, H. U. Ross

A generalized rate equation for the reduction of iron oxide was derived from which two particular equations were obtained: one for rate controlled by the transportation of gas, the other for rate controlled by the phase-boundary reaction. Pellets of pure ferric oxide having diameters of 8.5 to 17.5 mm and a density of 4.8 g per cm3 were prepared and reduced by hydrogen at 750° to 900°C. From the analysis of data obtairzed, it was observed that neither the phase-houndarv reaction nor the transportation of gas controlled entirely the rate of redziction. Rather, the mechanism of reduction can he divided into three stages. In the beginning, the process seems to depend predominantly on the surJrce reaction, hut after a layer of iron is formed the diffusion of gas becomes the controlling factor. Towards the end, however, the rate falls sharply due to a decrease in porosity. The times predicted by the generalized equation for a certain degree of reduction showed an excellent agreement with those obtained experinmentally for pellets of varying sizes. WIDE interest in iron oxide reduction has resulted in many valuable studies pertaining to thermody-namical properties, equilibrium diagrams, and chemical kinetics. Although the thermodynamical properties and equilibrium diagrams are now known with a fair degree of accuracy, the mechanism and rate-controlling step in the reduction of iron oxides presents a problem to research workers which is still unsolved. This is because the field of chemical kinetics is so highly complex. Besides the chemical reaction between oxide and reducing gas, several other processes are occurring simultaneously such as solid-state diffusion of iron through intermediate oxides (FeO and Fe3O4), the diffusion of reducing gas inwards and of product gas outwards, and the sintering of iron if reduction is carried out above the sintering temperature of iron. Furthermore, there is a large number of variables, including the nature and flow rate of the reducing gas, the chemical composition and physical properties of the ore, the temperature of reaction, particle size, and so forth, all of which can affect both the mechanism and the kinetics of reduction. Despite the controversy and diversity of opinion about the mechanism of iron oxide reduction, three main schools of thought have emerged. According to the first, the rate is controlled by the diffusion of gas through the boundary layer of stagnant gas; the second claims that the rate is proportional to the area of the metal-oxide interface, while the third believes the transportation of reducing gas from the main stream to the metal-oxide interface and of product gas from the metal-oxide interface to the main stream to be the rate-controlling step. 1) The boundary-layer theory is true mainly for packed beds where the flow of gas through the bed is important. For a single particle, the boundary layer may be prevented from being the rate-controlling step if a gas flow rate of reducing gas above the critical flow rate is used. 2) Several workers have reported a linear advance of the Fe/FeO interface which provides excellent support for the belief that reduction is controlled by the surface area. McKewanl has given formal shape to this concept with mathematical derivation and has shown it to be valid for reduction of several iron ores, hematite, and magnetite, both by H2 and H2, H2O, N2 mixtures. Some other investigators, however, do not find this theory to be entirely valid. Deviations have been observed2 and further confirmedS3 Hansen4 also agrees that deviations do occur, at least in the latter stages of reduction, while from the data of several investigators summarized by Themelis and Gauvin,5 it is clear that the theory is not always applicable and further that, when it is applicable, it does not hold in the final stages of reduction. 3) Among those who claim the transportation of gas to be the rate-controlling step are Udy and Lorig,6 Bogdandy and Janke,7 and Kawasaki el a1.8 The validity of the theory has also been acknowledged indirectly by other research workers who show that the sintering and recrystallization of iron cause a decrease in reduction rate, for it is only if the transportation of gas is important that this sintering has any bearing. However, the theory has been rejected by some because they have failed to obtain

Jan 1, 1965

By Fred T. Towne

There are a number of air classifiers manufactured throughout the United States and the rest of the world. The classifiers manufactured by Alpine, A. G. of Augsburg, Germany, are unique in their abilities. It is this uniqueness that I wish to delve into and in this respect we will limit this discussion primarily to the classifiers as manufactured by Alpine. It has been reported in the past that these classifiers were introduced into the. United States in the late 50&apos;s. Until the introduction of the Alpine Classifiers, air classification seldom produced a satisfactory fractionation of a product below 45 microns (325 mesh) or above approximately 22 mesh. It has been a common practice to classify fine materials which used water as a carrier medium The use of centrifuges are today producing thousands of tons of finely partitive powders in the very small particle size range. The use of centrifuges in connection with wet grinding mills has increased the rates of production of these mills considerably.

Jan 1, 1965

By K. M. Rolls, R. M. Rose, H. B. Shukovsky

Studies of the phase structure, critical current density, and resistive critical magnetic field of a 45 pct Nb-55 pct Zr superconducting alloy after final-size heat treatments are reported in this paper. A combination of optical metallography, X-ray diffraction, and electrical-resistivity measurements were used to determine the phase structure. Superconductivity measurements, made with heat-treated wires, are correlated with microstructure. Although no quantitative relationship between microstructure and critical current density is found, it is shown that SINCE Kunzler1 as well as Berlincourt, Hake, and Leslie2 first described the high-field, high-current-density superconductivity of Nb-Zr alloys, it has be- the critical current density is highest when the microstructure is finely divided by fibering, coring, precipitation, or fine-scale phase dispersions. The resistive critical field is very sensitive to the compositions of the phases present. Since the alloy investigated here is near the maximum resistive critical field for the Nb-Zr system, any phase decomposition results in a lower H,. Elimination of the effects of cold work lowers H, also. A possible interpretation of the latter in terms of internal surface superconductivity is suggested. come apparent that the resistive critical field and the current-carrying capacity of such alloys are, in large measure, dependent on composition and processing. The resistive critical magnetic field (Hr) for low current densities has been found to increase progressively with zirconium content until a flat maximum is reached between 50 and 65 pet Zr.3 For any single composition, a characteristic maximum value of H, is attained by heavily cold-drawn wire.4 critical current density (J,) depends not only upon cold work but also, apparently, upon microstructure. Heat treatments of cold-worked wires generally

Jan 1, 1965

By James D. Brown

The Bureau of Mines has written a computer program in FORTRAN to facilitate the calculation of concentrations from X-ray intensities in electron probe microanalysis. Philibert&apos;s absorption and Castaing&apos;s secondary fluorescence corrections are used; no atomic number correction is included. Background and dead time corrections are applied to the data before calculating the relative intensities. Data from any type of electron probe microanalyzer can be used with the program.

Jan 1, 1965

By P. Marier, T. R. Ingraham

When anhydrous cupric sulfate is heated in a stream of nonreactive gas, cupric oxysulfate is formed. When this reaction is complete, the cupric oxysulfate then decomposes to cupric oxide, which is the normal end product of reaction. The kinetics of each of these reactions has been studied using pellets prepared from finely divided cupric sulfate and from finely divided cupric oxysulfate. In each case, the reactant-product interface within the pellet is well-defined, and by normalizing the decrease in inter facial area with the weight fraction of the pellet decomposed it has been shown that the interface migrates into the pellet at a uniform rate at constant temperature. The activation energy estirnated for the decomposition of cupric sulfate is 57 ± 7 kcal per mole and that for cupric oxysulfate is 67 ± 8 kcal per mole. The rate of interfacial reaction is flow-sensitive, increasing with increasing flow of a sweep gas in the range from 50 to 2000 cu cm per min. The rate of decomposition is retarded by sulphur trioxide in the sweep gas. The relationship between sulfur trioxide Partial pressure and rate is consistent with the Langmuir Adsorption Isotherm governing the retention of sulfur trioxide in the interfacial layer. MOST of the work reported on the thermal decomposition of cupric sulfate and of cupric oxysulfate is related to the thermodynamics of the individual decompositions.&apos;-4 No information is available on the rates of the individual reactions, on their activation energies, or on the effects of gas flow or of partial pressure of sulfur trioxide on the reaction rates. Some dubious conclusions based on relative reaction rates have been drawn from studies on the oxidation of sulfides. For example, on the basis of the products observed in a quenched system, it has been suggested5" that, when copper sulfide is roasted, the cupric oxide which is formed arises from the decomposition of either cupric sulfate or cupric oxysulfate. This is very difficult to reconcile with the thermodynamics of the C-S-O System,3 which support the probability that both cuprous oxide and cupric oxide precede cupric oxysulfate and cupric sulfate in the sequence of products formed during the oxidation of cuprous sulfide. In this paper the individual sulfate decomposition reactions will be examined and suggestions will be advanced for the mechanism of reaction. This will be based on the effects on reaction rate of changes in interfacial area, flow rate, and back-pressure of sulfur trioxide. EXPERIMENTAL Materials. The copper source material used in all experiments was Fisher Certified Reagent Grade anhydrous cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared by roasting cupric sulfate for 48 hr, with frequent rabbling, in an open tray in a muffle furnace maintained at 725°C. At this temperature, cupric sulfate develops about 0.16 atm pressure of combined sulfur trioxide, sulfur dioxide, and oxygen. Cupric oxysulfate develops only about 0.05 atm pressure, and is stable until

Jan 1, 1965

By J. B. Gayle

The Bureau of Mines studied the effects of air oxidation on the recovery of float coal. Both batch-and continuous-type tests were made on six bituminous coals, representing the range in rank of coals now commercially used for carbonization, and on one anthracite coal. The effects on flotation recovery of oxidation at 1000 C for periods up to 50 days were investigated using an alcohol-type frother and a kerosine-pine oil reagent. Two series of release analysis tests were made, using one medium-volatile bituminous coal. Float coal recovery was adversely affected by oxidation in all tests where the alcohol-type frother was used. Conversely, a small degree of oxidation improved recovery with kerosine-pine oil frother for some of the coals in continuous tests. Prolonged oxidation (beyond about 14 days) adversely affected float coal recovery for all coals, the effect being more pronounced for batch-type tests and for tests using alcohol-type frother. Reagent selectivity for the rejection of both ash forming and sulfur bearing minerals was reduced by oxidation. Severe reduction of reagent selectivity required only about 3 days&apos; oxidation for alcohol-type frother but more than 10 days&apos; oxidation when the kerosene-pine oil reagent was used.

Jan 1, 1965

By John F. Elliott, John R. Rawling

The rate of reduction of silica to silicon by carbon at 1550° to 1700°C in iron blast-furnace type slag-metal systems has been investigated. In the tower portion of the temperature range oxygen transport in the metal boundary layer at the slag-tal interface is probably rate limiting. A second step, which apparently involves a chemical process in the slag at the slag-metal interface, appears to be rate limiting when the oxygen-transport limitation is avoided. Above 1650°C rate control of the reduction by carbon probably is mixed between the two steps. INVESTIGATIONS1.2 into the equilibrium distribution of silicon between graphite-saturated slags and metals typical of iron blast-furnace practice show that, under the experimental conditions specified, the reduction of silica to silicon is relatively slow compared with the rates of other slag-metal reactions under similar conditions. For this reason, the reduction of silica in blast-furnace slag-metal systems was considered to be an interesting subject for further study. Investigations of the kinetics of the reaction3-5 suggest that several possible steps may be rate controlling, and that the rate-controlling step depends not only on the physical state of the systems but also on the configuration of the apparatus. The main objects of the investigation reported here were to sug- gest plausible reaction paths for the reduction of silica under the experimental conditions chosen and to determine the step or steps which control the rate of reduction of silica. EXPERIMENTAL Two types of experiments involving the reduction of silica from the slag were carried out. In the first, the only reducing agent present was carbon (graphite), for which the over-all reaction is (SiO2) +2C(gr) —Si + 2Co(g) [l] The second type was a graphite-saturated ferro-silicon-iron concentration cell. In it silica in the slag could be reduced either by carbon according to Eq. [I], or by a reaction of electrochemical nature in which silicon was oxidized at the ferrosilicon-slag interface and silica was reduced at the slag-iron interface without the formation of CO. The two types of experiment are described below. Reduction of Silica with Carbon as the Only Available Reducing Agent. The reduction of silica was accomplished by allowing a liquid lime-alumina-silica slag and graphite-saturated iron to react in an induction-heated graphite crucible. The crucible was 2.25 in. diameter and 5 in. deep; it was fitted with a graphite stirrer which penetrated through the slag and into the metal, Fig. 1. The slag and metal charges weighed 350 g each. Pure carbon monoxide at a pressure of 1 atm was maintained above the melt by passing the purified gas through the crucible at a rate of 0.5 liter per min. The gas did not stir either the slag or metal. Temperature measurements were made by sighting an optical pyrometer down the hollow stirrer rod into a 1/4-in. hole drilled in the stirrer blade. The crucible temperature was maintained within *15"C of the required value by manual control of the power supply to the

Jan 1, 1965

By D. L. Feucht, R. L. Longini

The semiconductor heterojunction is considered in terms of simple models which may lead to an understanding of move complex heterojunctions. Metallurgical and electrical properties of hetero-junctions aye discussed including the interface structure, energy -band diagram, and carrier transbovt across the interface. It is found that in a heterojunction all mechanisms such as injection, tunneling, and junction recombination found in simple junctions play modified voles. INTERFACES between materials (grain boundaries, the electrical junction between two differently doped materials in a single crystal, the oxide-metal interface, or metal-metal junctions) are of considerable importance in many situations. These various interfaces all have one very fundamental thing in common. Quantum mechanically speaking, the wave functions of the electrons in one material may penetrate the other material but, in general, only to the extent of angstroms. From an electrical point of view the conduction mechanism changes as a current passes through such junctions. In some cases the change is tremendous, in others almost negligible. The interface, then, is the locus of a change of conduction mechanisms. Some of these, particularly in semiconductors, are well-understood. The ordinary p-n junction in a single crystal can be the locus of an injection mechanism or a tunneling process, depending on conditions. The mechanisms are probably best understood in semiconductors because of the possible simplified view of particlelike conduction. The bands are either nearly filled or nearly empty and band overlap is seldom involved. The same fundamentals are probably important in other situations too but they are very difficult to look at naively. Although the simple look at the semiconductor case only gives us a relatively rough picture which must then be refined, the other systems, which involve a more complex situation, immediately are in many ways too difficult. There are too many initial choices of complex systems and therefore it is not possible to be even reasonably certain of any one model. Because of the relative simplicity of semiconductors, their good and controllable structure, and because of the ability to make many measurements on them not normally available to either metals or insulators! they are probably the best understood materials. It is therefore desirable to use them as a tool to further the understanding of interfaces in general. Semiconductor-heterojunction concepts were first proposed by kroemer1 in 1957. This was followed several years later by reports on the fabrication and experimental characteristics of heterojunction structures by Anderson2 and Diedrich and jotten.3 I) THE HETEROJUNCTION STRUCTURE To get down to hardware, when we refer to a semiconductor heterojunction we imply that there exists an intimate contact between different semiconductor materials. We could put two pieces of material together, complete with oxide layers, we could remove the oxides, or we could even melt the interface and hopefully get wetting and a good "bond" on solidifying. In fact we could by some means grow a crystal of one material using the other as a seed. Essentially we are interested only in the last two because they are the simplest to look at analytically. The degree of perfection of fit varies greatly and is reflected somewhat in the arc welder&apos;s joint strength. The lattice match of the two materials, their orientation, and so forth. is obviously necessary for a good bond but so is the continuity of any polar bonds which are involved such as in the III-V semiconductors. The mechanical misfit between two similar lattices can be described in terms of edge dislocations. The edge-type dislocations must be very close together for the usual misfit and there must be dislocations for each of several different Burger&apos;s vectors in order to produce a lattice match. The .&apos;dangling bonds&apos;&apos; resulting will be involved in producing interface charge. Order of magnitude estimates of the charge density extrapolated from low densities of dislocations in homogeneous materials give 5 x 1013 cm-2 Ge-Si and 1 X 1012 cm-2 Ge-GaAs electronic charges. Edge dislocations also act as very active recombination centers between holes and electrons. One lattice "matching" difficulty usually exists even if two structures have essentially the same lattice constants as they will have different coefficients of therma1 expansion. Thus, on cooling from the usually high temperature of fabrication to room temperature, dislocations are produced, a good fit not existing at both temperatures. In brittle materials this shrinkage may even result in cracking. For the Ge-Si interface the mismatch is about 2 x 10 -6 per degree whereas it is less than 10"7 per degree between germanium and GaAs. The exact effect of the misfit is dependent on the thickness of the materials involved. For a very

Jan 1, 1965