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By Fred P. Giese

Southeastern reserves of titanium ores are large, widespread, and ample for anticipated demand. The leading titanium industries are mining and beneficiating sand deposits, principally in Florida, and manufacturing titanium pigments. Most of the mineral output is consumed by the producers themselves. In 1962, 20 percent of the national pigment capacity was in the Southeast.

Jan 1, 1964

By C R. Crook

A brief outline of production methods and processes is given to show how maintenance fits into the picture at this plant. The work force, and the tools needed to carry out this function, are then described. Preventive maintenance practices, scheduled annual shutdowns and routine check-downs are explained, especially as related to planning and to the materials and labour involved for a mini-mum downtime. A brief explanation of the materials, sup-plies and spare parts program, as well as the part played by the Stores Department in conjunction with the Maintenance Department, is given. Cost control and equipment expenditure indicators are explained. Some specific examples of maintenance jobs are described in order to show the flexibility of the program. S HERRITT GORDON Mines Limited has been in continuous production, except for the planned downtimes needed for expansion tie-ins, or the annual shutdown check-over periods, since the first shipment of nickel on a commercial basis in July of 1954.

Jan 1, 1964

By M. S. Burton, G. V. Smith, A. Rosen

The kinetics of re crystallization and the effect of recovery on recrystallization of pure iron were investigated within the temperature range of 517" to 632 OC. Grain growth and activation energies were also studied. Two stages can be distinguished during recrystallization; the first is gvowth-controlled and the second is nucleation-controlled. The extent to which the first stage succeeds before the second stage begins depends on both temperature of recrystallization and temperature of recovery. The softening of cold-worked metals and alloys due to transformation of the deformed crystals to strain-free equiaxed grains during annealing is well-known, and early inestiators established that recrystallization kinetics is strongly influenced by minute quantities of impurities. Generally, it is believed that impurities decrease the rate of recrystallization and the rate of grain growth. To understand the basic phenomena of recrystallization, investigations should be on pure materials. Most of the research on high-purity materials has been on metals having the fee Bcc materials, and especially high-purity iron, have been studied only in recent years. It is known that recovery may influence recrystalliation;" however, no general description of the influence, applicable to all materials, has been presented. This paper presents results of a study of the recrystallization kinetics of high-purity iron, after 60 pct cold deformation by drawing, with particular reference to the influence of recovery on the rates of recrystallization and grain growth. From observations of these rates, conclusions are drawn concerning nucleation. MATERIAL AND EXPERIMENTAL PROCEDURE Preparation of Material. High-purity iron, prepared by zone refining of vacuum-melted electroiytic iron at Battelle Memorial Institute under sponsorship of the American Iron and Steel Institute, was used in this study. Table I gives the reported chemical analysis of the material, taken at a point near the last molten zone and thereby rep- resenting the maximum impurity level for the entire bar. Prismatic specimens, approximately 10 x 10 X 50 mm, were sawed from the 50-mm-diam bar, perpendicular to the zone-refining direction, and turned to cylindrical shape. These specimens were sealed in quartz capsules under vacuum, approximately 10"e mm Hg, austenitized at 930° C for 15 min, slowly cooled, removed from the capsules, and cold-worked in air by swaging to approximately 20-pct reduction of area. The encapsulating, austenitizing, and swaging operations were repeated two additional times, after which the samples were encapsulated, austenitized, and cold-drawn to 60-pct reduction of area. A further vacuum anneal at 630°C for 120 min and cold drawing to 60-pct reduction of area produced wire 2.8 mm in diameter. The drawn wire was electropolished to remove deformed material on the surface, after which it was sawed into 4-mm-long specimens for the recrystallization study. Microscopical examination before the final cold reduction revealed equiaxed grain structure with very fine grains in a thin layer near the surfaces of the specimen and nearly uniform ASTM 3-4 grain size in the center. Recrystallization Heat Treatment. a) Direct Recrystallization of Cold-Worked The 60 pct cold drawn iron specimens were recrystallized at five temperatures, 517, 556, 590°, 612, and 632C, in a lead bath covered with graphite (the temperature was controlled to 1°C). Specimens were treated for twelve different times at each temperature, and all were water-quenched after heat &eatment. b) Recrystallization Following Preliminary Recovery Heat Treatment. After cold working, specimens were sealed into quartz capsules under vacuum, 105 mm Hg, and recovery-annealed at 362", 400", and 440°C for 20 hr prior to recrystallization. No evidence of recrystallization was found

Jan 1, 1964

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

By A. K. Mukherjee, John E. Dorn

The effects of strain rate and temperature on the critical resolved shear stress for (321)[111] slip were determined for the silver-rich CsCl type of intermetallic compound AgMg. The flow stress increased only slightly as the test temperature was first decreased below room temperature; a rapid increase in the flow stress was obtained with yet further decrease in temperature from about 250' to 4OK. The effect of both the temperature and strain rate on the flow stress over the low-temperature range could be rationalized satisfactorily in terms of the Peiwls mechanism when the deformation was controlled by rate of nucleation of pairs of kinks. IN spite of the well-documented interest of metallurgists and engineers concerning the mechanical behavior of intermediate phases and intermetallic compounds, very little definitive information is available on this important subject. As recently summarized by westbrook,1 only limited and modest progress has been made thus far in elucidating the details of the mechanism of plastic deformation for the intermetallic compounds; the available information largely concerns phenom-enological descriptions of empirical observations and experimental facts, principally with reference to poly crystalline aggregates. The present report on the elucidation of the rate-controlling mechanism for slip in the bcc structure of AgMg is part of the comprehensive program of a systematic investigation on the mechanical behavior of intermetallic compounds. The intermetallic compound AgMg has a CsCl type of lattice structureZ and is completely ordered up to its melting point of 820c3 This material was selected for our present investigation because of its simple crystal structure, moderate and congruent melting point, ordered structure persisting up to the melting point, and some solubilities of the constituent elements, which could be expected to help in the growing of single-crystal specimens. Whereas previous investigations on the properties of AgMg include hardness,*"6 slip systems,7 tensile flow stress of polycrystalline specimens,' and electrical resistivity,4 the current investigation will be directed principally at elucidating the rate-controlling dislocation mechanism responsible for slip in single crystals at low temperatures. It will be shown that the strain rate is consistent with a model involving the rate of nucleation of pairs of kinks by the Peierls mechanism for plastic deformation. EXPERIMENTAL TECHNIQUES Single-crystal specimens of the AgMg intermetallic compound were prepared and tested as follows: 1) A master alloy ingot of AgMg was produced by melting and chill casting the high-purity silver (99.995 wt pct) and high-purity magnesium (99.997 wt pct) in an induction furnace under a helium atmosphere. 2) Sections of the above-mentioned ingot were placed in a graphite mold containing a spherical cavity in which a single-crystal sphere of 1 in. diam was grown under helium by the Bridgman technique. 3) The operative slip systems were investigated at room temperature on a singlecrystal of AgMg, from measurements of the angles made by the slip traces on the two surfaces of the specimen, which were at 90 deg to each other. The investigation confirmed that the AgMg compound undergoes slip primarily in the (321) plane and in the [Ill] direction, but a small amount of secondary slip was also noticed in the (112) (111) system. No slip was observed in the (110) planes. 4) The single-crystal sphere, mentioned earlier, was oriented in a graphite mold containing a cylindrical cavity of 3/8 in. diam above the spherical receptable to give the angle xo = 45 deg between the axis of the cylindrical bar and the normal to the slip plane (321), and the angle AO = 45 deg between the slip direction [Ill] and the axis of the bar. Oriented single-crystal bar seeds were produced by melting, under a helium atmosphere, a polycrystalline bar in the cylindrical cavity above the oriented spherical seed and by growing an oriented single-crystal bar from the seed. 5) Finally, oriented single-crystal specimens were grown from these cylindrical seeds. 6) The cylindrical specimens were machined in a High-Tension Spark Cutting unit to give a 2-in. gage length. The spark-machined gage section was elec-tropolished in a bath containing 200 ml of H3PO4,

Jan 1, 1964

By Walter Kawa

Bureau of Mines research on the hydrogenation of coal has been concerned with developing processes that could be used to supplement the Nation's petroleum and natural gas resources. Motor fuel was produced in a subsidized coal hydrogenation industry in Europe prior to 1945, but the process used is still not economical and other methods of producing liquid and gaseous fuels from coal are being investigated. As an aid to the planning of coal hydrogenation research, a literature survey was made of processes or methods of hydrogenating coal that differ from the subsidized or conventional process. This report contains a bibliography of unconventional methods of hydrogenating coal and a brief discussion of the economics of the conventional method. A general discussion of unconventional methods is included, and the advantages and disadvantages are pointed out where possible. The survey supplements a previous Bureau of Mines survey3 and a comprehensive review published in 1930.4

Jan 1, 1964

By Burke Trafton

An earlier paper1 introduced a rapid solution for mine ventilation network problems, employing the digital computer. In this paper, refinements and additions to the computer program which expand its scope of application and a solution to a ventilation network having a coal-mine configuration are presented. Specifically, the revised program--written in FORTRAN for the IBM 7074 computer in Penn State's Computation Center--is applicable to any mine ventilation network employing natural splitting and having its fan located externally. It accomplishes the following; 1. Distributes an assumed total quantity of air flow among all air- ways of the network, performing iterations until an acceptable level of error is attained and the flow in each airway is known. 2, Computes the pressure drop (head loss) in all airways and the overall network and mine head losses. 3. Determines the operating point for the mine and a given fan, adjusting all air flows and head losses to the actual values.

Jan 1, 1964

By D. L. Ritter, N. J. Grant, B. C. Giessen

Forty-six alloys covering the complete concentration range of the Nb-Rh system were examined by metallographic and X-ray methods; solubility limits of terminal ad intermediate phases and transformation and solidus temperatures were determined. There are nine intermediate phases; two eutectic, five peritectic, two eutectoid, and three peritectnid reactions were encountered. The experimental methods and the constitution diagram are described in Part I. Part 11 deals with the crys -tallography and relation of the intermediate phases. The Nb-Rh system was selected for study for three reasons: first, it was hoped that the anticipated similarity of the Nb-Rh phase diagram to the Ta-Rh1 and Ta-Ir2 diagrams treated earlier (see also Ref. 3) and to the Nb-1r4 diagram treated simultaneously would allow a crystallographic and comparative evaluation of the intermediate phases in these related systems; second, it was likely that the previous experimental methods could be carried over without significant change; and third, it was expected that the interesting mechanical properties of the a1 phase of the Ta-Rh and Ta-Ir systems would also be encountered in similar phases of the new systems, and that these phases could be investigated more closely. The phase diagram had not been treated fully in the literature; only brief surveys of some intermediate phases were found.5-7 It was attempted to cover the details of the phase boundaries, Part I, as well as to present the crystallography of the intermediate phases, Part 11. EXPERIMENTAL METHODS Specimen Preparation and Treatment. The following high-purity starting materials were used. 1) Niobium powder, 99.8 pct pure, mesh size -60 +200, from Wah Chang Corp., Albany, Ore. The analysis furnished by the supplier showed the following major impurities: Ta, <500 ppm; Zr, <500 ppm; 0, 300 ppm; Fe, 280 ppm; Ti, <I50 ppm; W, Si, <100 ppm; C, N, 30 ppm; all other impurities, <30 ppm. 2) Rhodium powder, ground sponge, 99.9+ pct pure, mesh size -80, from J. Bishop Co., Malvern,

Jan 1, 1964

By E. O. Lilge, H. Siebert

A design of a multiple-bomb leaching unit particularly suited for the study of heterogeneous reactions, i.e. sol id-liquid-gas interfaces at high temperatures and pressures is presented. The component parts and overall design are described and illustrated in detail. The system has been tested by a limited number of experiments and found to work satisfactorily. Heterogeneous reactions at solid-liquid-gas interfaces, at high temperatures and pressures, are studied in either autoclaves1&apos;4 or bombs5&apos;9. Autoclaves are usually fairly large vessels which have a stirring arrangement incorporated in the design. Mechanical design limits the use of these vessels to relatively low temperatures and pressures. They are particularly well suited to rate or kinetic studies. Bombs can be designed to be operated at high temperatures and pressures, and are smaller vessels; because of this, stirring arrangements are not easily incorporated. In this paper a multiple-bomb system is described, that has been designed to incorporate the desirable features of both the autoclave and the bomb. The described unit has flexibility for an over all study of leaching. Most of the component units in this assemblage are standard equipment, designed and produced by well known manufacturers. No claim is made to the design of this equipment, and although described in some detail, this is done merely for clarity in the elucidation of the system presented. The general layout of the multiple-bomb assemblage is shown in Fig. 1A and 1B. The basic units in this system are: 1) 6 stainless steel 100 ml bombs (Fig. 4)

Jan 1, 1964

By Thomas Pollard

It is truly remarkable how the image of longwall as a method of mining has changed. Between 1920 and 19609 viewed on a world wide basis, longwall was regarded as a&apos; system for difficult and deep conditions and associated with intensive labour extraction. Today the world looks on longwall in the hope that it can produce the next really big break through in productivity, Three correlated machinery developments have made this possible, but it is not only the machinery developments, interesting though these be in themselves, but together with developments in control systems of these machines that longwall now looks so much more attractive, The machinery concerned is, of courses:- 1. The Anderton Shearer Loader - A miner that takes a narrow strip off the, face at rates acceptable to modern mining engineers. 2. An Armoured Flexible, Conveyor which can be kept in close contact with the face and still convey coal as it is snaked over to the faces 3. Powered support systems which can be mechanised and controlled with reliability at any distance from the individual support itself.

Jan 1, 1964

By William A. Beck

This report describes the loading and transportation practices employed at the zinc-lead mines of The Eagle-Picher Co., Jo Daviess County, Ill., and Lafayette County, Wis. The report also gives a brief history of the Illinois-Wisconsin zinc-lead district and the operations of the company in the area. The diesel-powered, rubber-tired loading and haulage equipment is described and illustrated from the operational point of view only, and an analysis is made of the materials-handling system without going into health and safety Factors. The costs per ton of the various components of mechanical loading, underground haulage, underground crushing, and hoisting for fiscal year 1960 are tabulated.

Jan 1, 1964

"The ore currently being milled at Delnite is a high pyrrhotite ore with the gold intimately associated with the pyrrhotite. To get maximum recovery of the gold with the lowest reagent cost, it is necessary to keep the pH as low as possible In the laboratory the best results were obtained with a pH of 10 but in the plant it was found that a pH of 11 was the minimum practical pH. With the n1anual control it was difficult to maintain this figure.The Mines Branch had a conductivity probe (see Fig. 1), developed by Dr. G .G. Eichholz that they wished to try out in plant operation.On June 17, 1963, the probe with all necessary control equipment was installed in the regrind circuit (see Fig. 2) at Delnite Mines. Crushed quick lime is fed at this point but it is also necessary to feed hydrated li1ne at two other points in the cyanide circuit in order to maintain the pH close to 11. 0 throughout the circuit. Only the feeding of the quick lime at the regrind mill was controlled in this test.One thing that concerned me with the operation of the probe was whether the reading on the probe chart would correspond to the pH. A look at the graph accompanying this paper will show that except for very minor variations the graphs of the chart reading and the pH reading are parallel. The upper graph shows that the pH reading and the lime titrations also correspond and that the cyanide titrations appear to have little effect on the pH reading.Table 1 gives the results obtained for the two months before and after the instal1ation of automatic control as well as the two months of control. Unfortunately there was a decided change in ore just after the automatic controls were removed. There was much less pyrrhotitc in the ore than usual thus changing the need for lime and cyanide."

Jan 1, 1964

By R. P. Smith

The diffusivity of carbon in iron, cobalt, and alloys of 89.7 and 79.3 wt pct Co has been determined by a decarburization method for the temperature range 850° to 1100°C. The Plots of log D us 1/T for the two Fe-Co alloys are linear through the region of the Curie temperature, showing that, unlike some cases of substitutional diffusion, carbon diffusion in these alloys is not affected by electron spin order. RECENT investigations1-&apos; have shown that for substitutional diffusion in iron the change in diffusivity with temperature does not follow an Arrhenius equation, at temperatures near the Curie temperature. Data on the diffusivity of carbon in a iron5"9 indicate that this anomaly does not exist for interstitial diffusion; however, this has not been definitely established. Since cobalt and Fe-Co alloys, 80 to 100 pct Co, have Curie temperatures in a temperature range convenient for carbon-diffusion measurements they are suitable systems for studying the relation of interstitial diffusion and the Curie temperature. EXPERIMENTAL The carbon diffusivity, D, was determined by a decarburization method. The diffusion cylinders, made from small vacuum melts of electrolytic cobalt and plastiron, were about 0.76 cm diam and 6.3 cm long. A small amount of carbon was added to each melt to keep the oxygen content as low as possible. The cylinders were first treated with a hydrogen-3 pct water vapor mixture at 1100°C to constant weight, then carburized to the desired initial carbon content with a suitable CO-C02 gas mix-

Jan 1, 1964

By T S. Cochrane

This paper is based on observations made during a recent visit by the writer to three of the dust research laboratories .in West Germany, each .of which is mainly concerned with studymg the composition and character of the respirable dust produced in mines or at industrial sites. The three institutes are discussed as regards their orgamzat10n and duties, their methods of dust sampling and analysis, and recent trends in research and development. An extensive bibliography completes the paper. Introduction A RECENT trip to Europe to attend international conferences m Austria and m Belgium gave the writer the opportunity to visit a number of research laboratories and mines in Western Europe. The visits to the dust research laboratories in West Germany are the basis of this report. In Germany, cooperative associations formed prior to and since the turn of the 20th Century to promote the safety and welfare of their workers have recognized the effects of airborne dust on the general health of the labour force.

Jan 1, 1964

By John Henderson

Densities of melts 0f the lime-iron oxide-silica system in contact with solid iron have been measured by the maximum bubble pressure method in the temperature range 1250° to 1440°C and the composition range 0 to 40 mol pct lime, 15 to 100 mol pct iron oxide, and 0 to 55 mol pct silica. Densities range from 4.65 g cm 3 for wustite at 1440°C to 2.75 g cm-&apos; at 1350°C for a melt containing 30 mol pct lime, 20 mol pct iron oxide, and 50 mol pct silica. The results are interpreted in terms of a postulate that the melts can be regarded as a random array of oxygen ions in which regions of local order exist to satisfy the coordination requirements 0.f the cations. An understanding of the nature of metallurgical slags is basic to the development of a sound theoretical description of heavy metallurgical extractive and refining processes. Because these liquids are complex, direct measurements of their properties has not thrown much light on their structure. This has led to the approach of measuring the properties of simpler liquids, and building up their complexity until slag compositions are reached. In this way the density of liquid iron silicates was measured in a previous study1 and the present work represents a further stage in this synthesis. EXPERIMENTAL The technique used in the measurement of density was the maximum bubble pressure method. Details of the apparatus and procedure were similar to those previously reported,&apos; with the exception that a constant voltage transformer was used to supply the power input to the furnace and six silicon carbide resistance elements were used in place of the molybdenum winding. With these modifications melt temperature could be maintained within 1 centigrade degree during the course of a run. The silica used to prepare the melts was washed natural quartz ignited at 1000°C; wustite was prepared by air-melting A.R. grade ferric oxide in an iron crucible and lime was prepared by air ignition, at 1000°C, of weighed quantities of A.R. grade calcium carbonate, previously air-dried at 110°C. The finely ground constituents were intimately mixed in a glass ball mill prior to melting. Temperatures quoted are accurate to * 5°C and the standard deviation of the density values, calculated by the method of least squares, ranged from 0.5 to 1.8 pet. However, replicate determinations of density on different melts of the same nominal composition at the same nominal temperature did not vary by more than 1 pct, Table I, and this figure has been taken as an estimate of the accuracy of the density results. The density of carbon tetra-chloride was also measured as a check on the absolute performance of the experimental method. At 20°C a value of 1.593 * 0.002 g cm"3 was obtained; this compares with the literature value2 of 1.595 g cm"3. Results of experiments designed to measure the dependence of the density of lime-iron oxide-silica melts, in contact with solid iron, on composition and temperature are shown in Table I. Because iron sometimes precipitated in the sample during quenching, the Fe203 chemical analyses were only poorly reproducible and should be taken as a guide rather than as absolute values. Fig. 1 shows the data from various sources for the density of liquid iron silicates and Fig. 2 shows isodensity contours at 1410°C for lime-iron oxide-silica melts, calculated by graphical interpolation of smoothed curves drawn through the experimental results, together with the 1400°C results of Adachi and ogino3 and Pope1 and Esin.4 Fig. 3 shows the isothermal variation with composition of the volume of melt per gram ion of oxygen at 1410°C and Fig. 4 shows regions in which the temperature coefficient of this volume is negative, positive, or negligible (<0.005 cm3 deg-I). DISCUSSION a) Disparity Between Reported Density Results. Consider the system iron oxide-silica, the results for which are summarized in Fig. 1. Although there is some difference in the temperatures at which the various densities apply, this difference is not sufficiently large to account for the observed discrepancies. The reliability of the present results for the low-silica region has been confirmed by measurement of the density of liquid wustite by three different techniques. At 1410°C the density measured by a balanced-column method was 4.55 g cm"3, by a combination balanced-column and gas-densitometer method 4.59 g emd3, and by a pycnometer method 4.53 g cm"3. Schenck, Frohberg, and Hoffermann&apos; have also reported a value of 4.55 g cm"3 for the density of liquid wustite at 1400°C. It must be concluded, therefore, that neither Pope1

Jan 1, 1964

By H. P. Ehrlinger

The Negociacion Minera Santa Maria De La Paz mining operations are located at La Paz (some eight miles West of Matehuala), State of San Luis Potosi, Mexico. These operations consist of a single copper-silver property, called the Dolores mine and a number of silver-low base metal properties. The ores from these several mines are transported by rail, or truck, to the central milling unit. The milling unit has two separate sections to treat the two types of ore. The ores from the several silver-base metal mines are mixed at the mill as they arrive. Up to the present time the silver-base metal ores have been milled to produce a bulk concentrate which carries valued in gold, silver, copper, lead, zinc, cadmium and considerable arsenic. In such concentration the zinc and cadmium values are lost to the operations in their liquidations as they are shipped as lead concentrates. Since these ores have exceptional quantities of arsenic which is concentrated in the milling process, these bulk concentrates have to be sent to a smelter for pre-smelting operations to remove the arsenic.

Jan 1, 1964

By A. W. Schlechten, A. H. Larson

Equilibrium H2S/H2 ratios were determined as functions of temperature (500o to 900°C) and composition in a hydrogen-circulation apparatus. Within the composition range studied there exists a two-phase region of "Zr3S4" and "ZrS2". The upper composition limit of this two-phase region is hounded by a disulfide phase and is practically constant over the temperature range investigated. The lower composition limit of this two-phase region is bounded a "Zr3S4 " phase and varies appreciably with tem- perature. The upper composition limit of the homogeneous region of the disulfide phase is not definitely determined, but it appears to he bounded by the stoichiometric composition of ZrS2. The lower composition limit of the homogeneous region of the Zr3S4 phase could not he determined due to the extremely low values of the equilibrium H2S/H2 ratios. Various thermodynamic quantities are evaluated from the data. PUBLISHED free-energy data for the Zr-S system are practically nonexistent. Strotzer, Biltz, and Meisel1 measured the sulfur pressures for the reaction 2ZrS2(s) + S2(g) = ZrS3(s) in the temperature range 783" to 874°C. The average heat of reaction calculated from the temperature dependence of the sulfur pressure is -47 keal. It should be noted, however, that according to these investigators, the two-phase region as determined by sulfur pressure constancy under isothermal conditions extended from approximately ZrS2, 3 to ZrS2.7. From consideration of X-ray data they concluded that the homogeneous regions of the disulfide and trisulfide phases are ZrS1.8-2.0 and ZrS2.8-3.2, respectively. Hahn and coworkers2 have made a structure study of the zirconium sulfide phases. They summarized the zirconium sulfide phases as follows: the compounds ZrS3 and ZrS2 with narrow homogeneous regions, a "Zr3S4" phase with a homogeneous region roughly within the limits of ZrSl.5 and ZrSo.9, the compounds ZrS and Zr4S3, and a "Zr3S2" phase with a homogeneous region within the limits ZrSo.8 and ZrSo.5. It is noted that the compounds ZrS and Zr4S3 are only formed in the gaseous state through sublimation of a phase which has the approximate composition of the compound. This paper describes the determination of the stability of the zirconium sulfide phases by a hydrogen-reduction method in which hydrogen is circulated over the heated sulfide until equilibrium is attained. The resulting H2S-H2 mixture is then analyzed. Partial molar free energies, enthalpies,

Jan 1, 1964

By K Morrison

Different individuals have calculated the boundary stresses around elliptical openings in an infinite elastic medium for various conditions of loading. With caution, such calculations are useful in indicating stress trends in mining. This paper illustrates an application to caving operations and suggests that abnormal field stress would have an adverse effect. Introduction GELDART and Udd (1), applying elastic theory, confirmed, and set out graphically, the stress distributions on the surface of elliptical openings with axis ratios varying from 1.0 (a circle) to infinity (a crack). The loading conditions varied from uniaxial to hydrostatic, and inclinations for the opening, with respect to the stress axis, varied from 0° to 90°. As most mine openings can be generalized into this elliptical conception, the usefulness of the presentation lies in the fact that given reasonable estimates for the stress ratio, the axis ratio, and its inclination, then the trend in stress concentrations as an opening develops can be readily approximated.

Jan 1, 1964

Cut and fillstoping using hydraulically placed mill tailings has become an essential feature of stoping operations in Kalgoorlie. &apos; Approximately 30 per cent of the total production is currently mined by this method. Fill is prepared by thickening or cycloning and is gravitated or pumped underground. The average pulp density is 70 per cent solids by weight, Recent cost reducing innovations are the use of steel passes, corrugated iron manways, polythene film sealing, and the replacing of vertical cement lined pipes with boreholes. TTTTTI rvr T Trim r l1TT

Jan 1, 1964

By H. B. Heller, T. J. LaChapelle

Phosphorus nitride has been used as a diffusant for introducing phosphorus into silicon under various conditions. It has a temperature -dependent rate of decomposition beginning in the 500°C range, increasing very rapidly above 1000 C, producing gas -eous phosphorus and nitrogen. Best control was obtained with a two-temperature arrangement, with silicon at the proper higher diffusion temperature. It is an easier compound to use than the usual P2O5 because it is nonhygroscopic and yields temperature-controlled surface concentrations together with excellent final surfaces. Surface doping nearly as high as that produced by phosphorus pentoxide has been observed for sources at 850" to 900°C. Reproducible high sheet resistances were obtained by using slow flow rates (1 linear in. per min) and staggered-baffle gas mixing with the nitride at 550°C. Both inert gas (argon, nitrogen) and oxidizing ambients have been examined. Oxygen reacts to produce anhydrous P2O5, consuming the source at a rapid rate. Nitrogen, except for short diffusion times, suppressed the dissociation reaction and sometimes produced inferior surfaces. Argon appears to be a more useful ambient. PHOSPHORUS is a common impurity atom which may be introduced into a semiconductor lattice to create a p-n junction or an nn contact region. Various investigators1-4 have described techniques which can be used with either elemental phosphorus or certain of its compounds. This paper discusses a newly available compound of phosphorus, phos- some processes silicon wafers are precoated with a phosphate glass which acts as the doping source. Although a nonoxidizing form like elemental phosphorus or a phosphine can be used, most diffusion methods usually involve the use of phosphorus pentoxide. Because of the rapid volatility of this compound, a two-step process is often used, combining a gaseous deposition to introduce a predetermined quantity of phosphorus into the silicon with a later redistribution to obtain the desired distribution and surface concentration. Such a process usually involves predepositing phosphorus at surface concentrations greater than 1020 cm-&apos;. At such doping levels the phosphorus-diffusion coefficient appears to be strongly concentration-dependent.596 Distribution profiles5&apos;9 for these high concentrations of phosphorus do not follow Fick&apos;s laws, having extended subsurface regions which appear electrically to be nearly uniformly doped with ionized impurity atoms. Radioactive-tracer experiments also show near-surface anomalies in the distribution profile. Additionally, it has been shown1&apos; that the introduction of very high surface concentrations of impurity atoms into silicon (a step necessitated by the subsequent lowering of concentration during the redistribution) creates dislocations, even in material having no dislocations originally. For device fabrication the use of oxide masking introduces certain difficulties and limitations.7&apos;8 The standard practice of using phosphorus pentoxide as an impurity source adds other problems to these because of the speed and ease with which this compound reacts with moisture present in any gas in contact with it. In fact, P2O5 is one of the fastest and most effective drying agents for gases. Because it is such an excellent desiccant, completely anhydrous phosphorus pentoxide is difficult to obtain and is even more difficult to keep dry. Adequately dry gloved boxes must be used for storage and transfer of the chemical. The presence of even traces of moisture will cause formation of phosphoric acids which, during the high-temperature diffusion, results in polyphosphoric acids of variable composition. Such reaction by-products end up as gradually accumulating viscous fluids in the cooler parts of the diffusion furnace. The calculation of the final solute distribution for

Jan 1, 1964