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By W. W. Anderson, S. Razi

Electroluminescetrce of single crystals of terbium-(loped ZnS prepared by vapor-transport technique shows the sharp line specirum characteristic of the 4f— 4ft,ansitiotzs of the trivalent Tb3 rotz. V-I tt~easuverr~ents give evidence of space-ellarge-lirrlited curvent but the thrveshold for trap-filled law behavior is not iu agreement with Lampert&apos;s theory for. Single injection. Variations of &apos;brightness with applied voltage, the observation of double peaks its brightness because joms, and the spatial distribution oi electroLur?zir~escerrce indicate that the accelet~atiotz-collision mechanism involving the bst lattice and/ov shallow traps is most likely to be responsible fov excitation of&apos; electrolnminescence. Efficiency rtreusuver)~etits show the quantwn efficiency to be about 10 pct and powev efficiency about 0.05 pct. Effect of anr~eallng the crystal in sulfur vapor is to enluztzce llle rare-earth emission. It rs pvoposed tlzat sulfitv anr~ealing crreates acceptorr-lvpe defects with which the donor-type vare-eavtll ion can associate more readily vesulting in enhanced rare-earth emission. A&apos;o such e~zlznr~cerr~etrt is obserued when the crystal is atztrealetl in zinc vapor. Photolianinescence of ZnS doped nith a variety of rare earths also shows tile slurvp l~rze rwve-eavtlz erriission which in sorrretirr~es accompanied by broad band, stvuctureless lattice emission. Photo-atrd electrolutr~itzesce?~ce of ZIIS:Tb slw~rj do!rlit~unt rare-earth emission in the ~ticirzity of 54(3OA corre-sporrdit~g to the transition D* — Fj. Hoz~!el)er, the detailed line structuve of the luo spectvtr is cliffevet~t, irzdicutit~g that different sites are active in the two processes. Decay of rave-eartlr fluorescence in ZnS doped with any of sei!evul vuve eurtlzs car1 be described by a single exporleritial e.scepl joy ZrlS:lIo. Tl~is exceptiotr can be explaitred it~ tevrr~s of tlre closely spaced er~evgy 1e1:els Jov the HO~&apos; iorr. Decay lime measurertzekzts jov ZnS:Tb, using pulsed elect,-ical ar~d pulsed opticcll excitutiorzs, (11-e itz goor1 agrcetrier~t. LUMINESCENCE of rare-earth-doped materials has been a subject of interest for the past 20 years. Within the past few years there has been a considerable increase in rare-earth research motivated in search of new and more efficient laser materials and also due to the use of certain-rare-earth compounds in the preparation of color television screens. The purpose of this study has been to seek an understanding of some of the basic processes involved in exciting the rare-earth luminescence which is associated with transitions within the 4f shell of the trivalent rare-earth ion. Single crystals of ZnS doped with a variety of rare-earth ions have been prepared by vapor-transport technique described elsewhere.&apos; Photoluminescence was excited by a high-pressure short-arc mercury lamp together with suitable glass and chemical filters. For electroluminescence, sinusoidal and pulse excitations were used. 1) ELECTRICAL CHARACTERISTICS 1.1) V-I Measurements. Electroluminescence experiments were performed on crystals of terbium-doped ZnS. The samples were cleaned and etched and indium or In-Ga alloy contacts were alloyed on by heating in H2 atmosphere to 600°C for times ranging up to 10 min. Static voltage-current measurements were made on several samples. Fig. 1 shows the results for a typical sample. For voltage V < 20 v, the V-I relationship is linear giving a resistivity of 2.5 x 109 ohm-cm for this particular sample at room temperature. In the range of 20 to 250 v, I varies as V "3 and at still higher voltages (when electroluminescence is visible to the scotopic eye) current varies as Vs up to 600 v, all at room temperature. At 77"K, for V > 200 v, / I vge5 up to 1000 v. The V-I characteristics at room temperature follow reasonably well the behavior predicted by Lampert&apos; for one carrier space-charge-limited current in an insulator with traps although, as shown later, the expression derived by Lampert2 for the threshold for trap-filled law behavior Vtfl yields an unrealistically low value for trap density if we use the experimental value of 300 v for VtfL. Assuming the case for shallow trapping, the transition from Ohm&apos;s law behavior to space-charge-limited behavior occurs at voltage Vtr given by where no = thermally generated free carrier density, L = length of the sample, e = static dielectric constant, 6 = ratio of free to trapped electron densities, e = electron charge. For the ZnS:Tb crystal, L = 0.5 mm, E = 8.3 €0, Vtr - 20 v, and no = 5 x 10&apos; per cu cm, calculated from the ohmic behavior assuming electron mobility of 100 sq cm per v-sec. This results in 9 = 0= As more and more electrons are injected the Fermi level moves up in the forbidden gap toward the conduction band. If we assume a single-energy level for traps (which is not strictly correct, as we will show later), the current voltage characteristic is profoundly affected when the Fermi level crosses the trap level. The traps are now filled and injected carriers can no longer be immobilized in traps. Hence, current rises sharply with voltage. The transition from space-charge-limited behavior to the trap-filled behavior occurs at voltage VTFL given by

Jan 1, 1968

By R. J. S. Brown, B. W. Ganison

A new logging method has been developed, based on measurement of the nuclear magnetism of formation fluids. The nuclear magnetism log (NML) is the only log that responds solely to formation fluids. It operates equally well in both oil-base and water-base muds and in empty holes, and can be used in all kinds of formations except strongly magnetic ones. Two separate NML measurements can be made, one of which provides a continuous formation fluid curve. This fluid curve is called the free fluid log (FFL) and is believed to indicate a minimum effective porosity in most formations. The FFL not only delineates fluid-containing zones, but provides an excellent correlation curve that can be obtained under conditions where conventional correlation logs are ineffective. Preliminary tests indicate that the second kind of NML measurement may help distinguish oil and water zones and provide information concerning permeability and wettability. (The FFL itself appears to provide some information on permeability.) The second kind of NML measurement requires stopping the logging tool for a short time opposite a zone of interest and taking more extensive NML data that can be displayed as nuclear magnetic relaxation curves. In some instances, oil and water saturations for the region immediately adjacent to the borehole can be read from these relaxation curves. INTRODUCTION In 1946, Bloch, Hansen and Packard and Purcell, Torrey and Pound3 independently announced the successful demonstration of the phenomenon of nuclear magnetic resonance. During the past 13 years, there have been many applications of nuclear magnetic resonance, including applications to the study of chemical structure and to the measurement of magnetic field strengths. Preliminary experiments on the feasibility of using nuclear magnetism measurements in well logging were made independently by California Research Corp. and Varian Assoc., the Varian work being sponsored by the Byron Jackson Tools, Inc. Since then a cooperative research program on nuclear magnetism logging has been carried out by the Byron Jackson Div. and Research Center of Borg-Warner Corp., and California Research Corp., subsidiary of Standard Oil Co. of California. The use of nuclear magnetism in well logging is of special interest because it offers a way of making direct measurements on the hydrogen in the formation fluids and not on the rock matrix. Within the past 1 1/2 years, successful measurements have been made with a research model logging tool in wells in California, Tex as, Utah, Louisiana and Wyoming. NUCLEAR MAGNETISM SIGNALS Polarization, Relaxation and Precession Many atomic nuclei possess magnetic moments and spins; that is, they are similar in some respects to bar-magnet and gyroscope combinations. Molecules and their nuclei are subject to thermal motion, which has a scrambling effect, tending to leave as many nuclear spins oriented in any one direction as in any other. However, if a magnetic field is applied, the magnetic nuclei tend to align in the direction of the field. The scrambling and aligning forces compete with each other, with the result that a few more spins are oriented parallel to the field than in other directions. This gives a net magnetization, or polarization, which is directly proportional to the strength of the applied magnetic field (aligning influence) and inversely proportional to the absolute temperature (scrambling influence). When the magnetic field in, or temperature of, a liquid sample containing protons is changed, the new equilibrium value of proton polarization is not established immediately but requires an amount of time which depends on the nature of the hydrogen-containing materials. The process of approaching the equilibrium value of polarization is called relaxation.&apos;.&apos; Polarization is a vector quantity, and the components parallel to and perpendicular to the magnetic field must be considered separately. Relaxation of the component parallel to the field is called "thermal relaxation", or "longitudinal relaxation", and the corresponding time for this component of non-equilibrium polarization to decay by a factor of e (natural log base) is denoted T. The relaxation of the perpendicular component is called "transverse relaxation", and the corresponding relaxation time is denoted T,. The potential energy of a magnet in a uniform field depends on the angle the magnet makes with the field; therefore, a change of the component of net polarization parallel to the magnetic field involves an exchange of energy between the spin system and the thermal motion of the molecules, leading to the term thermal relaxation for the relaxation of this component. Suppose we subject a sample to a strong magnetic field at right angles to the earth&apos;s field for a time greater than TI. A polarization, thus, is established at right an-

By Herbert Haas

ChEap power is essential to large-scale mining and metallurgical operations, particularly where fine grinding of large tonnages has to be resorted to, as is the case with an increasing number of mines treating disseminated copper ores, or low-grade gold ores, in the grinding of which considerable power is consumed. A comparison of the cost of generating power with Diesel engines and steam turbines and a brief discussion of the different factors governing the profitable use of either type of prime mover may be timely in view of the importance of a cheap supply of power to the mining industry, and the prominence that has lately been given to Diesel engines in America. As many of our most important mines and largest producers of metals are located in sections where neither cheap coal nor water power is available, and the price of oil fuel is increased by long hauls, the Diesel engine will become a prime mover of increasing importance. This applies particularly to the Southwestern States, where an ample supply of cold water for condensing purposes is unusual and local climatological conditions interfere in securing the high vacua essential to high turbine efficiency. About 12 times as much water will be required for condensing purposes with steam turbines under general conditions as is needed for jacket-cooling of two-stroke cycle Diesel engines; four-stroke cycle Diesel engines require only one-twentieth of the cooling water. Another condition favoring the use of Diesel engines is the high load factor at which most mine power plants operate. The influence of load factor on the cost of generating power is shown in Tables 1. and 2 and in Fig. 1. The higher the cost of fuel and the load factor, the greater will be the proportion of the fuel to the other costs making up the total cost of generating power. Capital charges (interest and redemption), maintenance, operating labor, and lubrication are practically constant amounts regardless of the load-output of the station; the fuel consumption and its cost are practically the only variables with the load. The costs here given are based on conditions as generally found in the Southwestern States, and on Diesel engine operating experience in European countries, where this type of prime mover has reached a high state of perfection, units upward of 4,000 hp. having proved entirely successful in operation.

Jan 1, 1917

By W. C. Lilliendahl, H. W. Highriter

The method developed and used in this laboratory for the production of metallic uranium of such purity that it is ductile and can be cold-worked to fine wire or thin sheet by rolling has already been described1. It consists, briefly, in the electrolysis of potassium uranous fluoride (KUF5) in a molten bath composed of equal parts of sodium and calcium chlorides. The bath is contained in a graphite crucible, electrically heated to about 775° C., the crucible serving as the anode for electrolysis. The uranium deposits in finely divided form mixed with salts upon a molybdenum cathode suspended axially in the crucible. Upon completion of the electrolysis the cathode is removed and cooled, the deposit broken and leached to remove salts. The metal powder is washed with water and dilute acetic acid and dried in vacuo to reduce oxidation. Suitable amounts are then prcssed into pellets and heated in vacuo by high-frequency induction, using a thoria crucible. The uranium melts and flows away from the pellet, leaving a shell, which is largely oxide. In general, this method produced a satisfactory metal, although at times tile uranium was not ductile. The investigations recorded here were made to find the cause of this embrittlement. It was known that the metal generally contained carbon, derived from disintegration of the graphitc crucible in which electrolysis is conducted, in amounts dependent upon the thoroughness of washing the metal powder. Accordingly, analyses of several samples, both ductile and brittle, were made by combustion and absorption of CO² in Ascarite, using air instead of oxygen to reduce the temperaturc and rate of oxidation. Several of these metals were made with special precautions to reduce carbon content. The results show no relationship between ductility and carbon content in the range investigated (Table 1). Microscopic examination of ductile and brittle metals disclosed the presence in the latter of an intergranular constituent, harder than the matrix and less easily oxidizable, which was absent from the ductile material. Rough estimates of the volume of the hard constituent

Jan 1, 1935

By W. C. Lilliendahl, H. W. Highriter

The method developed and used in this laboratory for the production of metallic uranium of such purity that it is ductile and can be cold-worked to fine wire or thin sheet by rolling has already been described1. It consists, briefly, in the electrolysis of potassium uranous fluoride (KUF5) in a molten bath composed of equal parts of sodium and calcium chlorides. The bath is contained in a graphite crucible, electrically heated to about 775° C., the crucible serving as the anode for electrolysis. The uranium deposits in finely divided form mixed with salts upon a molybdenum cathode suspended axially in the crucible. Upon completion of the electrolysis the cathode is removed and cooled, the deposit broken and leached to remove salts. The metal powder is washed with water and dilute acetic acid and dried in vacuo to reduce oxidation. Suitable amounts are then prcssed into pellets and heated in vacuo by high-frequency induction, using a thoria crucible. The uranium melts and flows away from the pellet, leaving a shell, which is largely oxide. In general, this method produced a satisfactory metal, although at times tile uranium was not ductile. The investigations recorded here were made to find the cause of this embrittlement. It was known that the metal generally contained carbon, derived from disintegration of the graphitc crucible in which electrolysis is conducted, in amounts dependent upon the thoroughness of washing the metal powder. Accordingly, analyses of several samples, both ductile and brittle, were made by combustion and absorption of CO² in Ascarite, using air instead of oxygen to reduce the temperaturc and rate of oxidation. Several of these metals were made with special precautions to reduce carbon content. The results show no relationship between ductility and carbon content in the range investigated (Table 1). Microscopic examination of ductile and brittle metals disclosed the presence in the latter of an intergranular constituent, harder than the matrix and less easily oxidizable, which was absent from the ductile material. Rough estimates of the volume of the hard constituent

Jan 1, 1935

By B. G. Slay, J. P. Pritchard, J. T. Pierce

A short discission is given of the cryotron us a supercozductitzg- switch. The parameters of interest such as gaiz, critical gate current, critical control current, and critical surface current density ave described. The photomask-photoresist process makes possible the study of much narrower dimensioned cryotrons than previously possible using mask stencils. Data is given for the above parameters as a function of width, thickness, temperuture, and crossing ratio. Photographs of the various circuits used are shown. The techniques involved in making connection to the circuits and the precautions taken to avoid side effects in the measurements are discussed. In particular data is given for critical currents of sipercotzducting. lines down to 2X 104 in. A vise in critical surface current density is obserced jor the strallev lines in both lead and tin. A discussion of the ihact of these measurements in the design of future cryotron circuitry is given. In addition to the improvement in device density achieved by simple scale reduction. additonal gains in density may result through improved device form factor. THE cryotron is a superconducting current switch, invented by D. A. Buck.&apos; Fig. 1 shows a typical crossed-film cryotron. Usually the gate is made of tin and the control is made of lead. The critical gate current, is the current that drives the gate resistive with zero current flowing in the control. The critical control current, I is defined as the current in the control necessary to switch the gate resistive with a small monitoring current in the gate. The gain of the device, G, is defined as Since for uniform thin films G should be proportional to the gate width divided by the control width, it is convenient to define the critical surface current density, Jcg, to be the critical gate current divided by the gate wldth. The data which follows will show that, for a given control width, I, is relatively constant. Thus, by measuring Jcg the change in gain as a function of gate width may be measured without measuring I,.

Jan 1, 1967

By S. F. Shaw

The theory that maintaining a high back-pressure on the oil sand lowers the viscosity of the oil has been generally accepted. The theory has also been advanced that lower viscosity permits the oil to be moved through the sand to the well at an expenditure of less gas per barrel of oil than would otherwise be required. It seems reasonable to assume that production of oil at the minimum gas-oil ratio will result in a greater ultimate recovery of oil. During the past five years the writer has acquired data on thousands of tests made on wells to determine the best rate at which to produce them. In the majority of cases reduction in back-pressure did not definitely increase the gas-oil ratio. The information obtained from these tests has raised doubt in the mind of the writer as to the correctness of the theory that lowered viscosity results in lower gas-oil ratios and in higher ultimate recovery of oil. The reasons that explain the results obtained in these tests cannot yet be definitely stated, but the hypothesis is being tentatively assumed that there are other factors which outweigh the influence of viscosity. Energy in Gas Moves Oil to Well The general opinion is that in most cases it is the energy in the gas that moves the oil to the well. In wells flowing naturally it is also the energy in the gas that lifts the oil to the surface. In a flowing well, there are two very distinct operations: 1. Moving the oil through the sand to the well. 2. Lifting the oil to the surface. The more important function of the gas is that of moving the oil to the well. Means for lifting the oil can always be found once it has been delivered to the well. Principles Involved in Lifting Oil A well that flows naturally is the same as a gas-lift well except that all of the gas is supplied by the oil reservoir. This natural flow is subject

Jan 1, 1931

By I. S. Levy, J. L. Brimhall, B. Mastel

Specimens of&apos; Hastelloy X-280, a low-cobalt version of the solid-solution- hardened nickel-base alloy Hastelloy X, were given a series of thermomechanical treatttzents. They were then Lensile-tested at room temperature and 1350°F. The Microstructures of the specimens tested at 1350°F were studied by electron Microscopy. Microscopy showed that dislocation tangling, caused by the cold working, mas still in evidence after aging-for 24 hr to temperatures as high as 1550oF. (Cr, Mo)23 C6, (Fe, Mo)6 C&apos;. as well us an unidentifiable phase precipitale due to the combination of the thermomechanical treatments and subsequent tensile strain. The room -temperature and 1350°F tensile properties show a general increase ill strength and decreccse in ductility with increusing cold-work level. This is due to the dislocation taangling-. PerLurbatiot~s to this general trend occur- due to solid-solution weakening at the higher cold-work levels as a direct result of the preciplitation reactions. THE requirements for corrosion resistance and high-temperature strength place nickel-base alloys among the more promising materials for advanced nuclear reactor applications. However, when these alloys are irradiated at service temperatures, they generally suffer severe embrittlement&apos;" and reduction in rupture life.3 Certain experimental treatments resulted in improvements in the tensile and stress-rupture properties of Hastelloy X-280, a solution-hardened nickel-base alloy.&apos; To provide a basis for understanding these improvements, unirradiated tensile specimens were examined by electron microscopy. The results are reported in this paper. EXPERIMENTAL DETAILS Material. Hastelloy X-280, a low-cobalt version of Hastelloy X, is a member of the solution-hardened class of nickel-base alloys. The Hastelloy X-280 was obtained from 4- and 1-in: thick plates in the mill -annealed condition. Table I gives the chemical composition of the material as reported by the National Spectrographic Laboratories. ~x~erimental Treatments. Plates of suitable size, 12 by 3 by 1 in., or by + in., were cut under a water jet from the stock material and examined ultrasonic -ally for homogeneity of grain size and absence of voids. The acceptable plates were solution-treated at 2150°Ffor 1 hr and air-cooled. These plates were then reduced in thickness by cold rolling 0, 10, 15: or 20 pct along the original rolling direction. The plates were machined into buttonhead tensile specimens with a gage diameter of 0.125 in., with a gage length of 1.125 in., and with their tensile axes parallel to the rolling direction. The specimens were examined for quality of finish with a penetrant dye, ultra son ically checked for voids, and finally given a dimensional tolerance check with an optical comparator. The acceptable specimens were aged for 24 hr at either 1000" or 1500 F and air-cooled. These specimens were then held at 540°F in a water loop for approximately 18 days to qualify as controls for similar specimens irradiated under the same conditions of time, temperature, water chemistry, and flow rate. Table U summarizes the treatments. These treatments were investigated to establish whether prior precipitation and stabilization of carbide phases at strain sites within the matrix could reduce the amount of carbides available for precipitation at grain boundaries during service. Tensile-Test Conditions. Specimens were tested to fracture at room temperature or 1350 F in air on an Instron tensile-testing machine at a crosshead speed of 0.05 in. per min. The time for the furnace to reach equilibrium at 1350°F was approximately 30 min; soak time prior to testing was 15 min; and test duration was approximately 5 min.

Jan 1, 1968

By C. P. Fiske

THE pottery of the New Jersey Zinc Co. (of Pa.) is equipped to make three classes of refractories; namely, spelter vessels, spelter condensers; and high-grade fire-brick. The most important of these are the spelter vessels, on account of the extreme severity of the service which they must perform, necessitating great care in the selection of materials and in the whole process of manufacture. Next to the spelter vessels in importance? come the condensers, as large numbers are used in the manufacture of spelter, and improvements m quality result in material decreases in working cost. , While the fire-brick which form the laboratory, or high-temperature portion of the spelter furnaces, are placed at the foot of the list, they-are nevertheless of much importance, since high quality will decrease the frequency of the always expensive shutdowns for repairs. To promote simplicity, the manufacture of these three products will be described separately in this paper, except in so far as materials and the crushing and handling system common to all are concerned. Materials Bond Clay.-The bond clay used entirely at the Palmerton pottery is a St. Louis clay furnished by the Grand View Fire Clay Co. It is stored in a system of covered bins, and no attempt is made to weather -it in the, accepted sense of the term " weathering." Some years ago our clay was weathered before pugging, but we did not find the benefit sufficient to offset the additional handling and the loss. of clay incurred. Furthermore, we believe that the rotting of the pugged mix (described later), accomplishes the same results to better advantage. That there is some action taking place in the clay while stored in the covered bins, however, is, evidenced by an increase in volume which at times has caused damage to the retaining walls of the bins. We have at present a stock of bond clay weathering in the open, and when this is put into service an opportunity will be afforded for making comparisons-with the clay as usually handled.

Jan 10, 1917

By J. D. Livingston

THE hardening of alloys by the precipitation of a second phase has long been an important technological process. One approach towards improving our understanding of this phenomenon has been a correlation of mechanical properties with such parameters as particle size and inter par ticle spacing.&apos; Several reviews of such data have appeared.2-4 A major limitation to this approach has been that for most alloys the particles are submicroscopic in size in the range of optimum hardness. Precipitation-hardening copper-cobalt alloys, therefore, are of interest, because the ferromagnetic properties of the precipitate make it possible to measure particle size, number of particles, and so forth, from magnetic measurements alone.5, 6 Livingston and Becker7 have applied these techniques to a study of precipitation hardening in an alloy of 2 pct Co in copper. It was found from magnetic measurements that nearly all the cobalt to be precipitated was out of solution within a few minutes at 600°C, whereas the peak in tensile yield stress was not attained until a much longer aging time. Thus during the first 1000 min of aging time at 600°C the Yield stress was increasing while a constant volume of precipitate was coarsening, i.e., while particle size and interparticle spacing were increasing. Peak yield stress was reached at an average particle radius of about 70A. The earlier study was confined to one alloy at one aging temperature, so that the volume fraction of precipitate was fixed and, therefore, particle size and interparticle spacing could not be independently varied. The work has now been extended to several alloys of varying percentage cobalt in copper, and to aging at various temperatures. It was hoped that such a study might clarify the relative importance to precipitation hardening of particle size, interparticle spacing, and volume fraction of precipitate. EXPERIMENT The alloys studied contained 0.7, 1.3, 2.0, and 3.2 wt pct Co in copper. They were prepared from electrolytic copper and electrolytic cobalt in a vacuum -induction furnace, worked to 3/8-in.-diam rod, and machined into tensile specimens with a gage section 1 1/2 in. long and 3/16 in. in diam. All specimens were given a solution treatment consisting of a 30-min anneal in nitrogen at 1000° C followed by a quench into iced brine. Subsequent aging was done in nitrogen and followed by a water quench. Average grain diameter was approximately 0.01 in.

Jan 1, 1960

By D. V. Doane, G. A. Timmons, W. G. Scholz

Molybdenum of high purity can be produced by direct dissociatiott of commercial molyhdenm disulfide in vacuo at 1600° to 1700°C (2910° to 3090°F). The Product is lower in oxygen than commercially available molybdenzdm powder. Analyses of ingots arc-cast from commercial molybdenum powder, hydrogen-re-cluced from animonium molybdate, and from thermally dissociated molybdenum disulfide indicate that the levels of chemical impurities in these ingots are similar. Equipment now in operation will produce 100-lb hatches of powder product. The paper describes development of processing equipment, control of processing varzahles, handling of the product, and evaluatiotl of the melal produced. MOLYBDENITE (molybdenum disulfide) can be decomposed by heat in the absence of oxygen to produce elemental molybdenum and sulfur, which is evolved as a gas. The temperatures required for the dissociation are above 1370°C (2500°F); the sulfur must be continuously withdrawn to permit the reaction to proceed to completion. This is accomplished by continuous evacuation of the thermal dissociation chamber and condensation of the gaseous sulfur in another part of the system. Cognizance of the fact that the dissociation takes place in two steps is important in controlling the process. Basically, the molybdenite dissociation process has two potential advantages as a method of produc- ing pure molybdenum: 1) The materials entering into the process contain little or no oxygen. Since the process is carried out in vacuum at high temperature, the quantities of interstitial oxygen, nitrogen, and hydrogen in the product should be very low. 2) The process is more direct than the commercia1 method of producing high-purity molybdenum. In the conventional process, molybdenite is roasted to molybdic oxide, the oxide is purified first by sublimation, then by conversion to ammonium molybdate, and finally, the molybdate is reduced in a hydrogen atmosphere (usually in two steps) to the metal lic molybdenum powder. This paper presents a description of the stages in scaling-up of the dissociation equipment and an account of attempts to evaluate the molybdenum produced by thermal dissociation, rather than a report of a fundamental study of the dissociation reaction. Since little has been written on the subject, it is appropriate, before detailing the development of the process, to review briefly the research that has been conducted over quite a period of years. LITERATURE SURVEY The first accounts of the possibility of thermal dissociation of the mineral molybdenite were re-

Jan 1, 1962

By F. P. Nichols, F. A. Renninger

At one time, mineral aggregates were considered physically and chemically inert substances whose junction was that of an inex-pensive, easily obtainable source of bulk. This philosophy applied regardless of the use to which the aggregate was put. Research approaches dealing only with such gross physical properties as hardness, toughness, impact resistance, etc., dominated the early growth years of the industry and influenced specifications to a large extent. The accelerated pace of highway construction, which began toward the end of the depression years, focused attention on the need for extensive aggregate research. The realization in the early 1940&apos;s that aggregates interacted chemically as well as physically with their environment provided the stimulus necessary to translate the drab, systematic aggregate technology of the early 20th century into the changing, dynamic, challenging field it is today. Current research problems are discussed in detail. These efforts being pursued by contract research organizations, universities, governmental agencies, and industry transcend many fields. The mineral aggregate industry is the world&apos;s largest mining and processing endeavor, yet it is graced with little of the romance or public awareness that accompanies mention of gold, silver, iron, copper, uranium, or aluminum mining efforts. Much of this reaction is undoubtedly due to the fact that the uses to which crushed stone and sand and gravel are normally put are not fully recognized or appreciated by the general public. Almost 2 billion tons of mineral aggregates are quarried or mined, processed, and sold yearly in the United States alone.= The largest uses to which this vast tonnage is subjected are as ingredients of portland-cement concrete, bituminous concrete, and dense-graded aggregate-base course mixtures in the highway and building construction fields, two industries closely related to the expenditure of public funds. It is for these uses, partially in justification for the expenditures of vast sums of public funds, that mineral aggregate research truly finds its emphasis. The research efforts expended relative to the highway and building construction uses to which mineral aggregates are subjected are those of primary concern to the industry. These efforts, while of direct consequence to the industry due to the volume market represented, are of interest as well to public agencies, universities, and contract research firms. All actively conduct research, exchange information, and make contributions to the overall knowledge relative to aggregate usage and limitations. The research efforts of the mineral aggregate industry is the subject to be discussed throughout this paper. It covers all aspects of highway and building design, construction, and technology. The effects of research pertaining to quarrying and mining methods, blasting and processing techniques, storage and handling facilities, and equipment employment and development have left their mark on the crushed stone and sand and gravel industries. Such specialized efforts have resulted in dramatically increased production rates which in turn have served to keep costs, and hence prices, down. Despite the many inflationary pressures over the years, the cost of a ton of aggregate today is little more than it was 25 or 30 years ago. Mention is made of these efforts simply to emphasize the diversity of research in the mineral aggregate field. The remainder of this paper focuses on the complexity of what might be termed "product knowledge" research.

Jan 1, 1971

By F. R. Archibald, C. M. Nicholson

THE present paper may be considered complementary to an earlier contribution on the same subject by F. R. Archibald and C. F. Jackson.1 It is particularly concerned with engineering and technological aspects of the operations at the Harleyville Alumina Plant during its period of operation from January 1945 to July 1946. The plant was built for and operated by Ancor Corporation, at Harleyville, South Carolina, as part of the government sponsored wartime program related to alumina production from domestic raw materials. The main purpose of the program was to secure technical and engineering data, based on actual plant experience, that might serve as a foundation for large scale production of alumina from raw materials other than bauxite. The Harleyville plant was directed specifically to treatment of clays found in very extensive deposits in the Carolinas and Georgia using the lime-sinter process developed by Ancor Corporation. It is considered that the purpose stated above has been served and this paper is to record and discuss some of the more important findings. The main factor in location of the plant at Harleyville was the presence in that locality of a rather remarkable deposit of high calcium limestone. The clay mining operation was centered near Aiken, S. C., and although a rail haul of ninety miles was involved there were, at the time, factors favorable to the Harleyville location offsetting, in part, the cost of transportation of clay. There are, no doubt, locations in the general area where clay and limestone deposits may be found in closer proximity but they had not been proven up when the project was undertaken. Availability of power from the Santee-Copper development whose high tension line skirted the property; ready access to rail and highway transportation; the promise, realized in actuality, of ample supply of soft water; and availability of labor supply were other factors of importance. Moreover, the general area has the decided advantage, for this type of operation, of a mild climate. Construction was begun in August 1943, and although stopped for a time pending review of the general situation that fall, it was resumed, albeit with less urgency, and substantially completed by the end of 1944. The total capital cost was approximately $3460,000. The first alumina was turned out in April 1945 and from then until the plant was closed down in July 1946, the operations followed a succession of periods of production alternating with periods in which minor alterations were made in conformity with experience. Steady improvement was made and at the time operations were discontinued it was considered that experience and the necessary engineering were in shape for removal of the remaining bottlenecks and a somewhat major revision in one section of the plant. Unfortunately this could not be carried out and it was necessary to discontinue the

Jan 1, 1948

By Henry Hebley

IN recent years, especially in the last decade, great interest has been shown and many advances have been made in the preparation and clean-ing of coal. In the major coal-producing countries, the percentage of tonnage cleaned has been increasing ever since 1924. As separating media, both liquids and gases are used, these generally being water and air respectively. Some systems, instead of obtaining separation by the velocity of the medium in which the coal is cleaned, depend on the density of water mixed with sand, or coal dust and shale, or with chemicals such as calcium chloride. In studying the results of coal-cleaning equipment, it will be observed that the efficiency of the cleaning apparatus lowers as the size of the coal decreases. This inability to obtain any marked improvement in the fines has been partly responsible for the installation of dedusting equipment, to remove the fine sizes from the raw coal prior to cleaning. When considering the possibility of installing dedusting equipment, many factors must be taken into account. Very often, but not always, both the ash and sulfur content of the coal increase as the coal size decreases. When bituminous coal, containing soft powdery fusain, is subjected to a wet washing process, the porous fines of the fusain remain in the small coal or in the wash water and delay the dewatering of the washed coal and increase the difficulty of clarification in settling tanks or thickeners. When a dedusted coal is cleaned by a wet process, the sludge recovered from the settling tank often runs so high in ash that the sludge can be discarded without further treatment and still the loss is small. Where treatment of the sludge is desired, however, froth flotation may be used to advantage if the size of the feed is below 1/10 in. Dust from the deduster can be treated in a similar manner. Fusain, which is usually found in the fine sizes, has often a much larger ash content than other coal.

Jan 1, 1933

By E. C. Tveter, L. A. Roe

The authors present a general outline of the theory and development of heavy-liquid application to mineral processing. Patent literature and processes are reviewed with special emphasis on liquid recovery systems which have been employed or proposed. Advantages and disadvantages of the process are discussed together with the recent developments which have revived interest in this old concentration method. The most important single factor in this resurgence of interest is concluded to be the narrowing gulf between chemical engineering and mineral dressing which has opened the field for new concepts of mineral plant design. A partial summary of patents on heavy liquid separations is included. In spite of the fact that heavy-liquid separation with organic liquids has been used in the laboratory for over 50 years, this process has never graduated to large scale commercial use for any extended period. However, a variation of this process, the sink-float or heavy-media separation process has found wide acceptance and is used to separate minerals from diamonds to gravel. Materials used to increase the specific gravity of the pulps used as heavy media include sand, clay, barite, magnetite, galena, hematite, atomized lead and ferrosilicon. Because of the greater ease of recovery, the magnetic materials, magnetite and ferrosilicon, are the preferred media today. In the U. S. alone, heavy-media iron ore plants with a capacity of over 10 million tons of concentrate per year are in existence. Heavy-media separation involving use of solid, inorganic particles suspended in water rapidly found a wide range of commercial use with the introduction of magnetic media. The minerals engineer is experienced in working with suspensions and quickly learned to develop and control such media at a cost compatible to the type of separation desired. The natural superiority of a heavy liquid with uniform chemical and physical properties has never been questioned since its first use in laboratory mineral separatory procedures. It offers the only method for gravity separation of fine particles of relatively close specific gravity. The most important early attempt to make heavy liquid separations commercial were made by the DuPont Co. which began experimental work on Virginia limonite in 1904. The appended "Partial Summary of Patents" compiled by W.L. O&apos;Connell of The Dow Chemical Co. demonstrates the quantity and sequence of this work. Both inorganic and organic parting liquids were investigated and numerous patents were issued on the use and recovery of these liquids. The work culminated in the heavy liquid plant of the Weston Coal Co. at Shenandoah, Pa. Chemical engineering design of this plant was the responsibility of Francis I. and Hubert I. DuPont. Heavy-liquid separation of coal almost achieved commercial status at this plant which actually processed over 20,000 tons of coal. The liquids used were tetrabromethane, pentachloroethane and trichlo-roethylene, with liquid losses ranging from 8.9 to 12.4 oz per ton of cleaned coal. The reasons for failure of this plant are not clear but probably involved toxicity problems as well as other problems in chemical engineering. Excellent economics were reported. A more recent pilot plant was built in 1954-55 by Norris Goodwin for the Inerto Co. to treat hectorite clay. This plant employed carbon tetrachloride in jigs with liquid recovery by evaporation. Although good separation was achieved, incomplete removal of the CCl, from the clay prevented commercial operation. The only present operations known to the authors employing heavy liquids for gravity separations are limited to the use of calcium chloride in certain coal washers and bromochloromethane in a small batch operation (one ton solids per day) for the separation of beryllium metal particles from slag materials. This is not strictly a minerals beneficiation problem but it has demonstrated the feasibility of such separations. PROBLEMS Critics of early attempts to commercialize heavy-liquid separation of minerals summarize the draw-

Jan 1, 1963

By N. A. Gjostein

The self-diffusion coefficient D, for a surface near the (100) plane in copper was determined by means of the Mullins theory of thermal grooving, and was found to obey the Arrhenius relationship, and Do = 6.5 x 10&apos; sq cm per sec. Suppression of surface diffusion by chemisorbed impurities encounters difliculties as a satisfactory explanation for the large Q, and Do. Instead, a model is presented which indicates that Q,, as determined by a mass-transport technique, may involve both the energy needed to form an adsorbed atom from a ledge in the surface as well as that for the movement of the adsorbed atom.; LITERATURE reviews1-3 indicate that the mechanism of self-diffusion on metal surfaces is not clearly understood. The lack of experimental data on the temperature variation of the surface self-diffusion coefficient DJ has contributed greatly to this situation. Radioactive tracer techniques4-rn have been used to measure Ds, but for many years only Nicker-son and Parker8 had determined (for polycrystalline silver) an activation energy B, and a frequency factor Do for the surface self-diffusion process. Even in this case, a mechanism could not be clearly inferred because it was suspeted7 that a contribution from volume diffusion was not taken into account by the investigators. Some later work by Li and parkere on polycrystalline gold, in which they obtained essentially the same results as for silver and in which volume diffusion could be accounted for, seems to invalidate this criticism. In 1957, Mullins10&apos;11 developed the theory for the thermal grooving process. This advance has opened a new and promising technique for measuring the surface self-diffusion coefficient Ds. Recognizing that a thermal groove may form by several different mass transport processes, Mullins first consideredlo the cases where a) the groove forms by evaporation and condensation or b) by diffusion along the groove surface, in either case, in a system where a metal surface is in contact with only its dilute vapor phase. In a later paper," he extended the treatment to cases where the groove forms by volume diffusion into c) the solid phase or d) by mass transport through a passive gaseous phase at 1 atm pressure. The time dependence of the groove dimensions and the shape of the groove profiles predicted by Mullins&apos; treat-

Jan 1, 1962

By Douglas Bunting

In the anthracite fields of Pennsylvania, mine fires occur with more or less regularity and their existence is an ever-present hazard in coal mining. In all probability 90 per cent. of the mine fires can be ascribed directly or indirectly to the ordinary miner&apos;s open lamp. Other causes may be smoking, electrical installations, gas explosions, gas feeders, and the communication of fire to the outcrops from ash dumps, culm banks, timber and brush fires. Fires in pump rooms, engine rooms, and barns have been largely eliminated as a result of the Act of Assembly, approved June 15, 1911, which provides that all inside buildings, including engine rooms, pump rooms, barns, etc., shall be constructed of incombustible materials. Smoking of pipes, cigars, and cigarettes should be prohibited in the mines and too much care cannot be exercised in preventing fires by enforcing all rules designed for that purpose. Mine fires that involve underground fighting are invariably dangerous, and all fires, irrespective of the method pursued in extinguishing them, involve property loss and expense. Each fire generally presents a more or less original problem, dependent on the particular conditions. Generally mine fires may be divided into two classes: Those occurring in inaccessible workings and those occurring in accessible workings. The methods pursued in extinguishing or controlling mine fires are as follows: (I) direct attack, (2) smothering by sealing, (3) flushing with silt or other solids, (4) flooding with water, (5) cutting off, (6) surrounding with incombustible materials, (7) digging out by stripping from the surface. Most fires arc extinguished in their incipiency by direct attack and failure to extinguish by this method is due to late discovery, lack of water, and facilities for fighting, or improper procedure in the initial attack. Should the method first pursued be unsuccessful, careful consideration should be given in determining next the method to be adopted; then the work should be carried on as rapidly as possible and under the supervision of the most competent persons. Materials and supplies should be furnished without delay and in sufficient quantities for the work to be accomplished.

Jan 1, 1922

By R. Fawley, M. A. Quader, R. A. Dodd

Stacking fault energies and annealing twin frequencies have been measured for austenitic stainless steels having a) constant 20 wt pct Cr and varying nickel contents, and b) constant 20 wt pct Ni and varying chromium contents. The effect of nitrogen has also been studied and, to a lesser extent, so has the effect of carbon. All measured stacking fault energies plot linearly against the corresponding annealing twin frequencies, suggesting that, for constant prior deformation and grain size, twinning frequency can be used to estimate stacking fault energy. Compositions low in nickel possess the lowest fault energy, while the maximum fault energy within the investigated composition range occurs mound 20 pct Cr-20 pct Ni. Nitrogen has practically no effect on stacking fault energy when increased from 0.005 to 0.05 wt pct, although Planar dislocation glide is associated with higher nitrogen contents; this may be a short-range order effect. Carbon may raise the stacking fault energy a little, and causes pronounced dislocation tangling in deformed alloys. The basically different dislocation structures promoted by nitrogen and carbon, respectively, are not associated with large variations in stacking fault energy, and the reason for the difference remains unknown. INTEREST in the dislocation configurations developed in plastically deformed alloys arises principally from a desire for an understanding of mechanisms of plastic deformation and fracture. Comparatively little basic work has been concerned with austenitic stainless steels, although considerable interest has developed in the fundamental aspects of deformation of these alloys since the suggestion that those compositions deforming essentially by planar glide are particularly prone to transgranular stress corrosion cracking.&apos; Certain facts are well-established. An 18 Cr-8 Ni steel (type 304) has a low stacking fault energy which is increased by higher nickel contents, and the structure of these steels when moderately plastically deformed changes concomitantly from planar to less planar to distinctly tangled dislocation configurations. These changes are thought to relate to changes in stacking fault energy, and considerable effort has been expended in measuring stacking fault energies of austenitic stainless steels through the determination of node curvatures2"4 even though the method has limitations due to formula approximations,5 an upper limit of measurement of 50 erg cm-2 at the most,5 and the necessity of an extremely meticulous experimental technique. Therefore, it is not surprising that only qualitative agreement between different investigators is generally to be found.&apos;-&apos; At high energies where node radius measurements are inappropriate, some use has been made of annealing twin frequencies to estimate relative stacking fault energies, although a recent critical evaluation of the method suggests that it should be used cautionsly with due regard to effects of grain size and prior deformation.6 Finally, there is a question as to whether the structures of some deformed steels are due to ordering effects. In particular, the role of nitrogen in promoting planar dislocation motion has been suggested to be due to ordering,&apos; but similar suggestions have been made for steels having low interstitial contents.4 EXPERIMENTAL Small ingots of austenitic stainless steels (-50 g) were prepared from components exceeding 99.99 pct purity, the nickel and chromium being Johnson Matthey "Specpure" metals. Carbon was added as pure graphite, and nitrogen as CrN. The components were accurately weighed, and it was assumed that the final composition was the same as the nominal composition

Jan 1, 1969

By Carl H. Schmuck

The terms "cable bolting," "extended ground support," and "grouted cable" are synonymous, and they have been popping up with much more regularity in the mining engineer s vocabulary. In simplest terms, lengths of u itensioned cable up to 18.3 m (60 ft) are grouted in drill holes prior to mining. This permits radical departures from mining practices that rely on conventional rock reinforcement. For example, by placing a pattern of cable bolts in the back of an open stope, ore can be mined in successive slices. After each slice is taken the protruding cable; are simply cut off and mining proceeds. When about 4.6 m (15 ft) of reinforced back remains, a crew places a new par tern of cable bolts in the ore.

Jan 12, 1979

By H. A. Wilhelm, P. Chiotti, G. A. Tracy

A summary of analytical, X-ray, thermal, and metallographic data obtained in the study of the Mg-U system is presented. No intermetallic compounds are formed by these two elements, and their mutual solubility is limited at temperatures up to 1255°C. The compositions of the liquids which coexist at 1135°C under a pressure of 3 atm are 0.14*0.05 wt pet U in magnesium, and 0.004 wt pet Mg in uranium. The solubility of uranium in magnesium decreases to 0.0510.03 wt pet at 675OC, and to about 0.0005 wt pet at 650°C. Due to the reactivity of both uranium and magnesium toward crucible materials, the choice of a suitable crucible presented a problem. Crucibles made from high purity magnesia to which 10 wt pet MgF2 was added to reduce porosity proved to be satisfactory. Some observations made with the use of other crucibles are given. THIS investigation was made to establish the phase diagram for the Mg-U system. Ahmann,&apos; formerly of the Ames Laboratory, did some work on the system. He used several methods in an attempt to prepare Mg-U alloys. One of the methods involved the reduction of UF, with a large excess of magnesium. In these experiments, the magnesium wet the surface of the uranium, but there was no evidence for compound formation. The maximum solubility of magnesium in uranium was indicated to be 0.01 wt pet. In another set of experiments, uranium chips as well as uranium powder were heated in contact with molten magnesium in a graphite crucible for periods of time up to 48 hr. A reaction layer was found at the Mg-U interface in several instances. X-ray analysis of the layer material showed the presence of UC and some additional unidentified lines which were interpreted as indicating the possibility of an intermetallic compound of uranium and magnesium. These studies indicated the maximum content of magnesium in uranium to be 0.043 wt pet. One sample of magnesium which had been heated at 1025°C in contact with excess uranium was found by chemical analysis to contain 0.275 wt pet U. Rules, based on empirical or semi theoretical considerations, which attempt to predict the alloying behavior of metals have been presented in the literature. Although these rules are not infallible, they nevertheless serve as useful guides. Using them, several generalizations can be made concerning the Mg-U system. According to Hume-Rothery&apos;s&apos; atomic

Jan 1, 1957