Search Documents

By Lyman Moore

This Bureau of Mines report describes 2nd evaluates iron ore resources in California and Nevada and analyzes the California and Japanese iron ore markets in which these resources will be used. The competitive position of California-Nevada ores, in these markets, was estimated by comparing regional iron ore prices, production costs, and transportation costs with those of foreign suppliers. Resources were determined to be sufficient to produce the equivalent of 585 million tons of 64-percent iron pellets at a price of less than $15 per ton delivered at California ports. Much higher tonnage could be produced at higher prices. Iron ore requirement of the California iron and steel industry will increase to an estimated 15.9 million tons by the year 2000. A study of the iron ore production potential of California-Nevada deposits and of out-of- State sources indicated that this ore requirement can be supplied most economically by California-Nevada ores. Iron ore import requirements of the Japanese iron and steel industry will increase to an estimated 150.0 million tons by the year 2000. A study of price trends in this market indicated that very little California-Nevada iron ore will be sold in Japan after 1973 when existing sales contracts expire. Iron ore-exports might be economically possible if ore could be transported from California to Japan at ballast rates as backhaul on existing petroleum shipping.

Jan 1, 1971

ABSTRACTFor the binary system copper-lead two relationsEquation 1andEquation 2have been derived for the activities of copper and lead at compositions and absolute temperatures within the liquid region of the phase diagram.These relations give, with greater accuracy than is given by previously published relations, the activity-composition temperature variations for all regions of the phase diagram of interest to metallurgists.These relations are essentially simple forms of the Margules equations but with linear temperature dependence applied to their coefficients. This has been done in such a manner that a phase diagram obtained from these relations agrees well with the data available for this system. The methods of obtaining the relations and constructing a phase diagram from them are both given in detail. The enthalpies and entropies of mixing are compared with those derived by other methods.

Jan 1, 1971

By L. K. Eigenbrod

Throughout the mining industry, pneumoconiosis is one of the most severe occupational health problems being faced. The goal of completely eliminating pneumoconiosis as an occupational health hazard was underscored by the Federal Government with its enactment of Public Law 91-173 (Federal Coal Mine Health and Safety Act of 1969). Under this law, permissible dust level standards will be placed at 2 mg/m3 in mine atmospheres by December 30, 1972. The mining industry is thus faced with the tremendous technical challenge of achieving this level. Two basic questions can be raised with regard to this legislation. First, does a maximum dust concentration of 2 mg/m3 prevent the occurrence of pneumoconiosis? Secondly, can this dust standard be achieved using presently available methods and equipment? A precise answer to the first question has not yet been developed by the medical profession. Studies are continuing on the origin, prevention, and therapy of pneumoconiosis, and permissible dust levels could become even lower as medical evidence accumulates. The mining industry has addressed itself to the problems of dust con-tro1 for many years as related to personnel health, explosive mixtures, visibility, and machinery damage. Dust control methods being employed involve

Jan 1, 1971

By W. Bleloch

Published in the Journal, September 1970, and presented at a colloquium on 'Future of the Steel Industry', 17th March, 1971. Errata (a) The final sentence in the penultimate paragraph, left hand column p. 34 of the text should read: 'In the hot regions of the bosh and stack the C+CO2=2CO reaction proceeds to CO from coke carbon and carbon dioxide generated by reduction of iron oxides by CO (the so-called solution loss of carbon)'. The italicised words have been omitted in the text. (b) Temperature in Fig. 3 is K not C. (c) In Fig. 9, connection from top plate of column 10 to heat exchanger 9 has been omitted. DISCUSSION J. B. BEEDON AND C. J. JONKER* Dr Bleloch's paper has outlined the advantages of recycling stack-gas of low nitrogen content in the blast furnace. In the first instance it would appear to be extremely beneficial in controlling the hearth temperature and allowing a 100 per cent oxygen-blast to be used. On a second point however we have to disagree. It is claimed that heat is liberated in the combustion zones by the oxidation of CO to CO2 near the tuyeres and in the subsequent reduction of the CO2 by CO. The author has hypothesized as follows, and we quote: 'The C+CO2=2 CO reaction in the outer combustion zone at about 1 700°C is no longer endothermic due to loss of stability of CO2 and its consequent dissociation into CO and free oxygen.' This statement requires closer examination. If we consider the individual events occurring with the CO in the recycled topgas, with the oxygen in the blast and with the coke in the burden, as done by Dr Bleloch, the following heat considerations emerge. All heats of reaction are calculated from the enthalpy values of each reactant and product, as well as the temperature dependence of their molar heat capacities. (a) At the tuyeres: CO+1/2 O2-+CO2 . . . . . (1) CO, CO2 at 500°C; O2 at 25°C. ?H reaction = -65 000 cals/mole CO The reaction (1) is exothermic. (b) In the outer combustion zone: CO2+C?2 CO . . . . . . . . (2) C, CO at 1 700°C; CO2 at 500 0C. ?H reaction = -56 000 cals/mole CO Reaction (2) is endothermic. The overall heat gain of reactions (1) and (2) is ?H=+56 000 - 65 000= -9000 cals/mole CO i.e. the overall reaction is slightly exothermic, the amount of heat liberated is however smaller than suggested by Dr Bleloch. (c) The dissociation CO2+CO+1/2 O2 . . . . . (3) is a highly endothermic reaction at 1 700 0C, requiring 82 000 cals/mole CO2 to proceed to completion. Furthermore, this reaction (3) is energetically not favoured to proceed, as can be observed from the free energy-temperature relationship of figure (3), which favours the formation of CO2 at 1 700 0C. Hence direct dissociation of CO2 at 1 700 0C appears to be unlikely.* The concept of recycling topgas is however still intriguing from many other points of view. Apart from providing a very efficient method of hearth temperature control, it will create a much higher CO partial pressure in the stack. Whether the rate of indirect reduction in the stack will be proportional to this partial pressure or not is un-

Jan 9, 1970

By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970

By R. L. Caldwell, E. E. Glenn, L. J. Norton, A. J. D. Straus, S. V. Holcomb, J. Zemanek

A new and unique logging tool, called the Borehole Televiewer (BHTV), has been developed to inspect boreholes and to evaluate formations. Even though geologists and engineers have had only about 3 years' experience with the BHTV, the thinking of many of them has been radically influenced by the fascinating and revealing "log-picture" recorded with the tool. The BHTV fills a need for a logging tool that can produce a direct and descriptive record of the physical properties of the borehole environment. Although primarily developed to evaluate fractured reservoirs, the BHTV has been used successfully to solve a variety of problems related to formation evaluation and borehole inspection. Geologists and petroleum engineers have been confounded for many years by the problems of locating and evaluating fractures. Interpretation of the usual resistivity, acoustic or radioactivity logs, as well as the analysis of cores, for evaluation of fractured reservoirs is extremely difficult and often not definitive. This is understandable since analysis of cores from fractured formations has reported variously: (a) low porosity, (b) no effective permeability, (c) lack of any matrix oil saturation and (d) oil stains on fracture planes as the only indications of potential production.14 In recent years acoustic amplitude logs have been introduced and used with varying degrees of success to locate fractures.8'9'11"13 Conventional amplitude logs at best give only qualitative answers where quantitative ones are desired. The logs reveal nothing of the orientation of the fractures. In addition to these logs, various types of cameras, television, and rubber impression packers have been used for borehole inspection. (See Appendix.) The BHTV logging tool supplies both the quantitative and the orientation answers about fractures. The borehole can be filled with any homogeneous, gas-free liquid such as fresh water, saturated brine, crude oil or drilling muds. This tool takes an "acoustic picture" of the borehole wall. The resulting log is a representation of the borehole wall as if it were split vertically and laid flat. The log is oriented with respect to magnetic north. Any physical changes in the borehole wall are seen as changes in picture intensity. In this way, fractures, deformation or pits are reflected on the log. Tool Description The fundamental parts of the BHTV are shown in Fig. 1. A piezoelectric transducer probes the borehole wall with bursts of acoustic energy. A flux-gate magnetometer senses the earth's magnetic field and provides the means for determining the orientation of the log. A motor rotates the transducer and mag-

Jan 1, 1970

By L. E. Cardwell

This publication contains routine analyses and related source data for 390 natural gas samples from 22 States and five foreign countries. Of this total, 385 samples were collected during calendar year 1969. The remaining five analyses are of samples collected during previous years, but releases granting permission to publish the results were not received until 1969. All samples were collected as part of a continuous survey of the free world for occurrences of helium in natural gas. This survey has been conducted in the United States by the Bureau of Mines since 1917. In late 1965, the survey was expanded to include foreign gasfields. The analyses published herein were made by mass spectrometer and a special helium analysis apparatus which are described in Bureau of Mines Bulletins 4863 and 576.4 Eleven previous publications have presented the results of 8,660 gas analyses made by the Bureau of Mines Helium Activity prior to 1969. The first three, Bulletins 486,6 576,6 and 617,7 contain analyses and related source

Jan 1, 1970

By G. B. Craig, H. E. Rosinger, W. J. Bratina

NUMEROUS studies have been reported on how the mechanical properties of a bcc metal are affected by interstitial solute atoms in the temperature range where appreciable diffusion occurs in finite time. Only recently, though, has work on an "interstitial-free" iron been reported, this by Leslie and sober,' on an Fe-0.15 pct Ti alloy. The data was limited to a maximum temperature of 296°K. This work presents a systematic study of the flow stress and the activation volume of a similar material as a function of plastic deformation over the temperature range 253" to 473°K. The material studied was Ferrovac E iron containing 0.01 wt pct C and 0.0002 wt pct N annealed at 870°C for 1 hr, and the same iron with an addition of 0.15 wt pct Ti annealed at 870°C for 80 hr; cooling rates being 75°C per hr. In the latter alloy depletion of interstitials in the a-iron matrix associated with the second phase formation was expected. The temperature dependence of the flow stress was measured at 6 = 3.33 x 10-5 sec-1 from 253" to 473°K as a function of the deformation in 0.01 intervals from 0.03 to 0.12 strain. Results for two strains, 0.03 and 0.09 are shown in Fig. 1. The flow stress increased and reached a maximum in the Ferrovac E iron with increasing temperature, but showed a consistent gradual decrease in the Ferrovac E-0.15 pct Ti alloy. A yield point and Luders region, observed in Ferrovac E, was absent in the Ferrovac E-0.15 pct Ti alloy. Also, the Ferrovac E exhibited a serrated stress-strain behavior in the temperature range 330" to 400°K; dynamic strain-aging characteristics were absent for the titanium alloy. The activation volume was determined over the same temperature range by the method of stress relaxation at constant strain. Results are shown in Fig. 2. At the temperatures of serrated stress-strain behavior in Ferrovac E the activation volume was found to increase toward infinity and, as the temperature rose, to decrease, to about 100 to 200 v/b3. By contrast, the activation volume for the Ferrovac E-0.15 pct Ti alloy tended to increase continuously from the initial value of approximately 300 at 300°K to more than 800 at 473°K. Above 400°K, then, the corresponding activation volume values of Ferrovac E were less than that of the Ferrovac E-0.15 pct Ti alloy. The activation volumes, Fig. 2, appear to depend on dislocation-interstitial interaction in Ferrovac E and on dislocation-dislocation interaction in Ferrovac E-0.15 pct Ti alloy. The gradual increase in the latter metal is associated with thermally activated motion of dislocation segments.' The decrease of the activation volume in Ferrovac E above 400°K is probably related to the diminishing effect of interstitials on dislocations. Here, the interstitials can be moved along with a dislocation without appreciable drag. As indicated in Fig. 1, removal of interstitials

Jan 1, 1970

By Herbert Dlaska

The BBU - rotary hearth treats lead concentrates and battery scrap by the roast-reaction process. It corresponds in principle to the long-known Newnam hearth, however its hearth-basin is not straight but curved to a closed ring. In operation this annular hearth is filled with liquid lead and rotates around a central blast-box. The charge, heated to a glowing-red, floats on top of the lead bath, into which air is blown from the blast-box through a horizontal slot-type tuyere. Ore pellets and brown coal are continuously charged onto the reacting mass from two storage bins. Lead is set free by the roasting reactions and trickles through the charge into the lead bath from where it is tapped from time to time. The reacting mass is continuously stirred by a mechanical agitator and backed, by a mechanical shovel, against the water-jacketed wall of the blast-box. The gangue of the charge forms lumps of scorified character, the so-called hearth slag or grey slag, which are discharged from the hearth. The waste gases are collected in a hood and conducted to a baghouse from where the fumes and dust are automatically transported to the pelletizing installation and are recycled with new material. The daily output of lead bullion depends mainly on the lead content of the charge. With lead concentrates containing 74% lead, about 24 tons of lead bullion per day are produced on the hearth at a direct lead recovery of about 89 per cent. Approximately 10 per cent of the lead content of the new material passes into the hearth slag from where it can be recovered in a blast furnace or in a rotary furnace. For small lead smelters the BBU-process represents the most economical way of melting high-grade lead concentrates. The process requires a relatively small capital investment, consumes little fuel, utilizes cheap fuel and is very flexible. Further, of great importance, is the fact that battery scrap can be treated by the BBU-process with very good results.

Jan 1, 1970

By B. B. Rath, Hsun Hu

In wedge-shaped bicrystals of zone-refined aluminum it is observed that (111) pure tilt boundaries migrate under the driving force of their own inter-facial free energy. The boundary velocity is a power function of the driving force. The driving force exponent decreases with decreasing angle of misorien-tation. For example, at 64O°C, the exponent decreased from 4.0 for a 40 deg to 3.2 for a 16 deg tilt boundary. An evaluation of the driving force acting on the boundaries during their motion indicates that for low driv-forces, up to about 2 x l03 ergs per cu cm, the velocity is relatively independent of misorientation, whereas at higher driving forces a 40 deg tilt boundary exhibits the highest velocity. The measured activation energy for boundary migration approaches that for bulk self-diffusion at low driving forces, decreasing from 33 to 27 kcal per mole as the driving force is increased from 1 x l0 to 5 x l03 ergs per cu cm. These results are compared with current theories of grain-boundary migration. In previous experimental studies of grain boundary migration the driving force has been limited to a difference in stored energy across the boundary. This stored energy has been introduced into the crystal either by prior deformation1-3 or by grown-in lineage structure. A part of the energy stored in the deformed crystal is released by recovery either prior to or concurrently with grain boundary migration, thus introducing an uncertainty as to the magnitude of the driving force responsible for grain boundary migration. The grown-in lineage structure, though thermally stable during annealing, neither provides conditions under which different levels of energy may be stored in the imperfect crystal nor provides a control of orientation difference across the migrating boundary of a growing grain. Furthermore, because of variation in the lineage structure, it is difficult to determine accurately the energy stored in the imperfect crystal. Several investigations of grain boundary migration during normal grain growth have also suffered from difficulties in estimating the driving force because of uncertainties in the principal radii of curvature.~ In the present investigation the velocity of pure tilt boundaries in zone-refined aluminum bicrystals of selected orientation (40, 30, and 16 deg around the [Ill] tilt axis) has been measured in the absence of a dislocation density difference across the moving boundary, thus eliminating the previous experimental difficulties. The driving force for boundary migration is derived from a gradient of the total interfacial free energy of the migrating boundary in wedge-shaped bicrystals. A similar method was attempted by Bron and Machlin in a study of grain boundary migration in silver. However, they found that one of the crystals was deformed and consequently the motion of the boundary was partly due to a difference of stored energy across the boundary. The observed behavior of boundary velocities as affected by the driving force is examined in the light of the predictions of the current theories of grain boundary migration.7"10 The effect of boundary misorientation on velocity is compared with the theory of " which is based on a dislocation core model for high-angle boundaries. EXPERIMENTAL METHOD Seed-oriented bicrystals of zone-refined aluminum, 2.5 cm wide, 0.5 cm thick, and 12 cm long, containing tilt boundaries with a common (111) axis, were grown from the melt in the direction of this axis. Spectro-graphic analysis, reported earlier,'' indicated the purity of the crystals to be 99.999+pct. Three such bicrystals containing 16, 30, and 40 deg tilt boundaries were used. Wedge-shaped specimens were prepared from these bicrystals by spark cutting followed by electrolytic polishing. The angle of the wedge was usually 40 deg and the specimens were usually 0.25 cm thick. The intercrystalline boundary was located within 0.2 to 0.5 cm from the tip of the wedge. Fig. 1 shows a section of an oriented bicrystal containing an outline of a wedge-shaped specimen. The crystallographic directions shown in Fig. 1 represent the orientation of one of the crystals (the larger section of the bicrys-tal); the orientation of the other crystal differs only by rotation around the common [lil] axis. The parallel faces of the wedge always corresponded to the common (171) planes in both crystals, whereas the orientation of the side faces varied, depending on the misorientation angle. The bicrystal orientations were determined

Jan 1, 1970

By Kenneth G. Colman

Even though wet processes were used in coal preparation plants prior to 1941, dewatering coal was not a problem then because the finer sizes were uneconomical to recover and were considered waste. However, during the war years the scarcity of raw materials necessitated the utilization of every pound of natural resources and coal plants began seeking an economical mans of recovering fine coal. Early efforts to this end concentrated primarily on centrifugal dewatering devices. Such equipment produced good results but was relatively expensive. In 1944, a method was devised utilizing a vibrating screen fitted with a profile wire deck rather than the standard woven wire cloth deck. This machine came to be referred to as a dewaterizer. Results obtained with the dewaterizer approached those of the centrifugal equipment, but at a lower capital cost, Their use reduced either the number of centrifugal units required to follow the dewaterizers or the required energy input to heat dryers, In some cases they eliminated the need for any further dewatering equipment.

Jan 1, 1970

By John P. Capp

Information is summarized on the major uses of fly ash and prospects for utilization in agriculture and in brick and mineral-wool manufacture. Technological aspects of utilization are discussed and references are given to the work of many of the leaders in the fields of fly ash production, processing, and utilization.

Jan 1, 1970

By Bernard Schneider

The diversity of methods available to engineers and geologists for studying rock masses is a reflection of the fact that, despite the rapid and encouraging progress made over the last few years, there is still no unified and comprehensive method which can be used to predict the over- all behavior of a foundation. Nevertheless, it is agreed that the fundamental characteristic affecting the engineering properties of rock is fissuration, and this paper de- scribes a few new or improved methods of studying fissuration and its influence on major engineering factors such as permeability, deformability, or internal stresses in the rock volume. TESTS ON SAMPLES Conventional tests on samples using thin slices can be improved by staining the slices before cutting with certain ionic dyes which have an affinity for certain types of surface. This shows up the microdiscontinuities. For example (quoted terms are French trade names) : "Turquoise Motylhne JSA" will show up porous alteration of basic feldspars. "Vert brillant SA" is used for acid feldspars. "Fushine ASA" will show up voids in all rocks. A mixture of "Turquoise" and "Rhodamine BSA" will show up zones of alteration in all types of feldspars. With this technique, it is easy to make an optical classification of the different structural types, e.g.: (1) rocks completely free from voids; (2) rocks with microfissures, which in turn can be subdivided into (a) rocks with microfissures secant to the mineral structure, (b) rocks with microfissures parallel to the mineral structure, and (c) rocks with ran-

Jan 1, 1970

By Foster Fraas

Under a very high vacuum of 10-8 torr the transfer of terrestrial mineral beneficiation methods to the vacuum ambient of extraterrestrial locations such as the lunar surface was investigated. In the size range for the electro-static and magnetic separation of ores (minus 35 plus 150 mesh) there is no adhesion of particles produced by crushing and grinding due to the limited contact area, and for repeated contacts area size has a frequency of occurrence in accordance to the normal law. The photoelectric effect which is successful in separating a few minerals in an air ambient has a wider application in a vacuum, while the lack of air viscosity and sound transmission provides for high feed velocities and the adaptation of particle vibration to dispersion and grinding. Contact electrification is reversible upon return to atmosphere.

Jan 1, 1970

By W. R. Wilcox

The camphor-anthracene system was chosen as a transparent low-melting analog of the zirconium carbide -graphite system. Camphor and zirconium car -bide both grow nonfaceted, while casting of mixtures yields platelets of both anthracene and graphite. Zone melting of thin layers of organic was observed under the microscope. Irregular lamellar structures were produced at high values of the ratio of the temperature gradient G to the zoning rate V. The anthracene invariably led the camphor, indicating lower kinetic undercooling for the anthracene. The lamellar spacing was an order of magnitude greater than typical spacings for metal eutectic systems. Exact behavior depended on orientation of the anthracene. Oriented dendritic structures were produced at low values of G/V. Transient and oscillatory behavior were also observed—much of it unexpected. A.RC-CAST refractory carbide-graphite mixtures are promising thermal-shock resistant materials. Oriented structures of these materials would be superior to arc-cast materials for many applications. Mollard and Flemings1 and Cline2 have shown that aligned structures can be obtained for a wide range of Pb-Sn alloys. However, these metals both solidify in a nonfaceted manner while graphite yields platelets or flakes. In addition only small diameter samples of Pb-Sn alloys were produced because it was necessary to avoid free convection and to have high temperature gradients. The purpose of the present work was twofold: 1) To observe the solidification of a transparent low-melting analog of carbide-graphite systems and 2) to see if larger diameter samples can be produced. EXPERIMENTAL PROCEDURE When zirconium carbide-graphite mixtures are cast, the resulting structure naturally depends on composition. Carbide-rich mixtures yield metal-like nonfaceted carbide dendrites in a eutectic matrix. Graphite-rich alloys have graphite platelets in a eutectic matrix. Empirically it was found that camphor-anthracene mixtures produce similar structures with camphor being nonfaceted and anthracene forming plates. The organic eutectic melted at 116°C and was composed of 78 wt pet camphor.3 The camphor used was U.S.P. grade from Fisher Scientific Company; the anthracene was 98+ pet fro Aldrich Chemical Co. The impurity content is judged to be on the order of 1 pet. Mixtures ranging from 50 to 88 wt pet camphor were employed for the experiments. All but one of the experiments were performed on the microscope-stage zone melting apparatus described in detail elsewhere.4 The organic mixtures were contained in horizontal cells made of microscope slides or cover glasses. In most of the cells the organic was present as a very thin layer, thus giving almost two-dimensional growth behavior. The cells were moved slowly under a heated wire, which caused a molten zone to move through the solid at rates ranging from 0.01 to 5.4 cm per hr. The temperature gradient was estimated before moving the zone by measuring the distance between the line where all solid was melted (freezing point) and that where solid first began to melt (eutectic temperature). The temperature gradient was found to be 465°C per cm in the thinnest cells used, which were made by pressing together two microscope cover slips in the organic melt and then rapidly withdrawing them. RESULTS The experimental results are described in four parts: simultaneous growth, dendritic growth, irregular growth, and transients and erratic phenomena. Steady state data are summarized in Fig. 1. Except where noted all comments are for the cells containing a thin layer of organic. A) Simultaneous Growth. Simultaneous and roughly parallel growth of anthracene and camphor was obtained over the full range of compositions investi-

Jan 1, 1970

This Bureau of Mines report reviews the development of the world potash industry. The trends leading to the present market situation of oversupply arid low prices, which threaten; the domestic potash industry, are presented and analyzed. Because the major threat to the domestic industry comes from Canadian imports, the report focuses on the comparative economics of United States and Canadian production. The study resulted in these major conclusions: 1. Balance of world supply and demand is foreseeable in 1975, but it could be delayed by planned expansion. 2. Balance of U.S. supply and demand could occur as early as 1974-75 or as late as 1981. 3. Nearly all U. S. production capacity vis-a-vis Canadian competition is now uneconomic. Prices cover out-of -pocket costs for only 30 percent of U.S. production. 4. U.S. producers will be undersold by Canadians in 60 to 90 percent of the U.S. market. Canadians also will have the edge over United States and European producers in export markets. 5. U.S. firms have invested in 60 percent of the planned 1971 Canadian production, and they have large holdings in Saskatchewan. 6. The decline in the U.S. potash industry probably reduced personal income in Carlsbad, Eddy County, N. Mex, the chief potash-producing area in the United States, about $21.5 million between 1966 and 1969.

Jan 1, 1970

By I. D. Shah

The Bureau of Mines investigated the sequence of principal chemical reactions taking place during the roasting of covellite (CuS). Practically all covellite is converted to digenite (Cul.SS) before oxidation to Cu20 begins. Part of the Cu2O is then converted to CuO, which in turn forms CuS04 through CuO?CuS04 as an intermediary. CuS04 and CuO'CuS04 decompose at 600° to 700° C to yield CuO and S03 (g) as final products. An overall mechanism is proposed for chemical reactions occurring at different interfaces of partially oxidized CuS pellets.

Jan 1, 1970

By C. J. Chindgren

A refractory-lined, garage-type automobile incinerator with a natural gas afterburner for air pollution control was cooperatively constructed and tested by the Bureau of Mines and the Wasatch Metal & Salvage Co. in Salt Lake City, Utah. The incinerator is capable of relatively smokeless burning of 32 to 60 cars per day, dependent on the degree to which the cars are stripped prior to incineration. Preliminary burning campaigns indicate the cost of incineration to be approximately $2.75 per car.

Jan 1, 1970

By L. B. Pankratz

Enthalpies above 298° K were determined for AgCl to 1,400° K and for AgBr to 1,200° K by copper-block calorimetry. Before melting, both compounds showed an anomalous increase in enthalpy, an effect associated with lattice defect formation. Melting points and heats of fusion were determined to be AgCl, 730° K and 2,945 cal/mole; AgBr, 700° K and 2,030 cal/mole. The heat capacity of both melted substances decreased with increasing temperature over the entire liquid ranges investigated. Enthalpies above 298° K were tabulated at even temperatures along with derived entropy increments and heat capacity values. The results were combined with the known heats of formation and entropies at 29.8.15° K to obtain values of the heats and free energies of formation over the range 298.15° to 1,400° K for AgC1 and 298.15° to 1,200° K for AgBr.

Jan 1, 1970

By C. J. Lewis

Considerable amounts of the world's known reserves of elemental sulfur are found near the surface in areas of volcanic activity both active and inactive. Because such deposits cannot in general-be mined by the well-known Frasch process, and because other methods of recovery have not proven to be economically competitive except in isolated instances, at present these reserves remain relatively undeveloped. However, projections of world sulfur demand indicate that new sources of marketable sulfur will be needed in future years 2/, 19/. For this reason, recovery of elemental sulfur from these near-surface deposits is of continuing interest. Solvent extraction as an approach to recovery of elemental sulfur from open pit-mined ores of these non-Frasch deposits has received considerable attention particularly at the research and development level 3 /, 7/, l l /, 16/, 21/,23/, 29/ This method has been and continues to be attractive because it presents the potential of high sulfur recovery and purity of product coupled with a relatively simple process flowsheet in which low energy requirements and reasonable operating costs are thought to be possible. However, the physical and chemical characteristics of the native-sulfur ores, of elemental sulfur, and of the known solvents, have presented difficulties in the development of solvent extraction processes. Up to the present time, viable processes have not been realized within the framework of sulfur marketing conditions.

Jan 1, 1970