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By M. I. Brittan

Discussion Dr R. E. Robinson (Fellow): The author must be congratulated on a very meticulous and self-contained piece of work. It is indeed a pleasure to read a paper that is so clearly and systematically laid out, and where the conclusions and the testwork conducted have been so clearly described. The paper is complete in itself, which makes it very difficult for someone who is not intimately involved in the whole Torco project to make any comments on its content. However, two points that, strictly speaking, fall outside the scope of the paper are of considerable interest. The first relates to the particle size of the material treated. In the paper, the testwork is confined to one standard particle size (minus 60 plus 100 mesh). The essential feature of the paper is to indicate that the rate-controlling reaction in the whole segregation process is the rate of reaction of the ore particles with the reducing agent and the hydrogen chloride. One wonders, therefore, to what extent this relatively slow rate of reaction is affected by the particle size of the ore itself. One imagines that the reaction must take place by contact of the hydrogen chloride with the surface of the mineral particles, and it is reasonable to suspect that the rate of diffusion of the copper ions to the surface is a relatively slow process and is thus the limiting factor in this particular rate of reaction. It is possible, for example, that the improvement obtained, when the ore is subjected to reducing conditions before the chlorination, is due to a breakdown in the crystal structure of the original particle. This breakdown is brought about by the reduction and by the consequent increase in surface area available for reaction with hydrogen chloride. Can the author indicate whether any work has been done along these lines, and whether it has been established that the reaction depends on the surface area available? The second point relates to the application of this kinetic study to the actual operation of a Torco reactor. It was once planned to feed the sodium chloride, together with the reducing agent, into the top of the segregation chamber. In the paper, the author mentions that it has now been established that the segregation chamber behaves, to all intents and purposes, as a fluidized bed, and that there is, therefore, a rapid evolution of gas in the lower regions of the chamber, which, it is imagined, displaces the gas phase rapidly. Since the reaction between sodium chloride, water vapour, and the aluminium silicates in the ore is extremely rapid, one wonders how much of the hydrogen chloride produced is removed from the reaction zone before it has had time to react with the copper minerals. The extremely low consumption of sodium chloride (which is a vital feature of the Torco process) must depend on an extremely rapid circulation of the hydrogen chloride gas to all the ore particles in the segregation chamber. One wonders, therefore, if a system for the introduction of the sodium chloride into the bottom regions of the chamber might not result in even greater efficiency in the utilization of sodium chloride. ProC D. D. Howat (Fellow): All of us who have been concerned with the study of chemical reactions at high temperatures are keenly interested in kinetics and are well aware that this is not an easy study experimentally. Dr. Brittan is to be congratulated on the development of neat experimental methods and for his full discussion of the results obtained. Although the segregation process for the extraction of copper from oxide and silicate ores has been known for almost fifty years, the fundamental chemical and physical changes involved have been little understood and the fundamental data are very scanty. The work now in progress at A.A.R.L., together with that sponsored by the Anglo American Corporation in other research institutions throughout the world, is bound to produce new fundamental data and a much more complete understanding of this rather fascinating process. It is already apparent that some of the old and well-worn chemical reactions that were postulated to occur, just cannot take place in the way which was formerly accepted. Dr Brittan's work, carefully conducted and thoroughly analyzed as it has been, still leaves us with one great outstanding problem. The thermodynamic data and the possible reactions set out in Table I (page 281) of his paper leave us asking, in complete despair, how can copper be converted into a volatile chloride in the presence of HCl, CO and carbon at temperatures about 800°C? The thermodynamics all combine to show that copper should be reduced to metal as the first step in the process. This brings us right up against the second problem. If copper were reduced to the metal how would HCI convert it to the volatile chloride? On top of these problems is the unknown reason for the very high speed of reaction between CO, HCI and the ground copper ore. Still further into the region of the unknown is the reaction by which gaseous hydrochloric acid is produced in the actual process. Perhaps Dr Brittan is feeling grateful that he doesn't have to try to explain this reaction-at this stage of the research programme at least. The results very clearly show that both CO and HCl gas are essential for rapid production of the volatile copper chloride. Dr Brittan states that 18 minutes were required to attain 83 per cent extraction with HCl gas alone and this was reduced to 4 minutes when CO was

Jan 2, 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 A. Bruynesteyn

I would like to talk to you today about microbiological leaching or, the solubilization of metal values due to the action of Thiobacillus ferrooxidans. Bacterial attack of sulfide minerals has been going on for centuries but only recently was it discovered that the acid and iron often found in coal mine drainage is produced by bacterial action on the iron sulfides in the coals. Not until 1950 was it proven that bacteria were playing a role in the dump leaching of sulfide ores. B. C. Research became involved in microbiological leaching in 1955 while examining mine drainage from the copper-zinc mine at Britannia Beach, north of Vancouver. Since 1955, B.C. Research has maintained a continuous re¬search program on microbiological leaching which, due to its applied nature, was put under industrial sponsorship in 1962. Most of the information pro¬vided in my talk today has been gathered under this sponsored research program and I would like to express our appreciation to the many sponsors who have made our work possible.

Jan 1, 1970

This evening I would like to speak about men for the mineral industry.It is trite to say that the mining industry is expanding rapidly and that technically trained men are in short supply. How short is difficult to assess and impossible to quantify.The industry has been traditionally managed by technically trained men experienced in the ways of their fellow men. Let us start with the assumption that men with this training and experience are essential to management of mining and metallurgical enterprises.I suggest that we do this as it avoids argument with those who are beginning to suggest that such men are not so important as they used to be; who are suggesting that the latest sophisticated business management schools can produce managers who can straight out of school join the upper echelons of an organization and successfully manage it by the use of modern systems and techniques without the need to rub shoulders with men of all callings and get their hands dirty in the process.This kind of thinking brings to mind the modern cargo ship which is equipped with all the latest gadgets of science. It can find its way from Sydney to Auckland with no one in the engine room and the man on the bridge spending most of his time writing to his wife or reading the latest novel.How often do we read of this ship being tied up in Sydney because the crew sympathizes with the cook who has been slighted by some uncomplimentary remark about his toheroa soup? Here is a pieceof sophisticated machinery stopped through no technical fault, but held up by the whim of man. The understanding of man by man can spell the success or failure of any endeavour. A single man can leadan organization to the pinnacles of success, or doom it to utter failure in spite of modern systems and techniques.So let us start from the point that people matter.Through the years our Institute has been fortunate in having many members who have felt strongly...

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 R. L. Vaughn, H. R. Cooper

Effective procedures for automating X-ray assaying by use of a computer are described. These methods have advanced the reliability and accuracy of X-ray data, resulting in improved assay measurements for operations and process control. Assaying by X-ray fluorescence has been increasingly used in the mining industry, both for analyzing solid H.R. COOPER and R.L. VAUGHN, Members AIME, are Systems Manager-Process Control and Senior Systems Analyst, respectively, Scientific & Engineering Computer Center, Ken-necott Copper Corp., Salt Lake City, Utah. TP 68B236. Manuscript, Sept. 16, 1968. Discussion of this paper, submitted in duplicate prior to Dec. 15, 1969, will appear in SME Transactions, March 1970, and AIME Transactions, 1970, Vol. 247. samples for smelter, mill, and mine quality control and for continuous stream analysis of mill pulps. The important advantages of X-ray methods in laboratory assaying are reduced analysis cost, and for on-stream analysis, immediate assay information on concentrator streams. Of the numerous reports concerning X-ray analysis in mining operations, one is referenced which can be noted particularly in conjunction with this report.' Continuous X-ray analyzers have been installed at Kennecott and other mining companies for operations guidance and trend information for a number of years. However, complete operational acceptance of X-ray data has been slow, due* to the difficulty in maintaining

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 William T. Ingram

Early in the 60's the author served as Chairman of the Engineering Foundation's Coordinating Committee on Air Pollution Research. One of our objectives was the development of a study on the measurement of stack emissions. Three publications of the Foundation resulted from these efforts to focus attention on the stack sampling problem.1,2,3 Two of these were annotated bibliographies covering 197 references. The third reported the results of a workshop meeting at which some 21 individuals from research institutes, industry and government discussed the possible and probable areas of research that would add to or increase the ease, precision and utility of sampling gaseous and particulate matter emitted from stacks. The American Society of Mechanical Engineers has had in its Power Test Codes a Standard Code for Determining the Dust Concentration in a Gas stream4 since 1941, The American Industrial Hygiene Association has published, in its Air Pollution Manual,5 a Section on Stack Sampling. Industry and regulatory agency requirements for stack sampling have utilized some modification of the alternatives in methodology. There has been ho single guide to stack sampling that met the needs of those who have the need to know.

Jan 1, 1970

By Eugene E. Brucker

In recent years, there has been increased interest in construction problems presented by karst topography. Twenty-five years ago, karst areas were by-passed for development. Today, the high cost of land and population pressures are requiring utilization of karst areas. Areas exhibiting karst features can be satisfactorily developed so that construction can proceed in a normal manner; or the areas may be left undeveloped and the underground drainage system abused by improper use causing or contributing to structural collapse, excessive erosion, and a grave threat to the stability of land development and the environment. The term "karst" is a comprehensive term applied to areas underlain by soluble rock that possess a topography formed chiefly by the dissolving of rock and the diversion of surface waters to underground routes. There are four features which contribute to the maximum development of karst. 1. A soluble rock, preferably limestone, must be present at or near the surface of the ground. Occasionally, dolomite will suffice.

Jan 1, 1970

By J. H. Swisher

Two recent papers in this journal1,2 contain experimental evidence for an anomaly in the concentration gradient for tracer diffusion. In both papers, the authors suggest that this anomaly is due to a Gibbs' absorption effect. Their hypothesis is that surface active tracer elements tend to remain in or near the surface adsorption layer, thereby altering the diffusion flux and concentration gradient. It is not clear how the anomaly can be explained in terms of an adsorption effect. Surface tension forces act parallel rather than perpendicular to a surface and therefore should affect only the rate of spreading of surface active agents tangentially across a surface. Frenkel3 has given a short treatment of surface tension as a driving force for surface diffusion. While the equilibrium concentration of a surface active agent at the surface of a solution is known to be higher than in the bulk, its chemical potential is necessarily the same. It is difficult to see how adsorption can result in an anomaly in the chemical potential gradient, which is the driving force for diffusion. A more detailed explanation by the authors of the adsorption mechanism is in order. A similar anomaly does not seem to arise where

Jan 1, 1970

By K. D. Sheffler, R. W. Hertzberg, R. W. Kraft

The Ni-Ni,Ti lamellar eutectic alloy responds to unidirectional solidification by alig-nment of the platelets of the two phases roilghly perpendicular to the moving solid-liquid interface. X-ray diffraction and zetallographic experimenls show that the following cryslallographic relationships exist in the directionally solidified ingots: lamellar interface w [0001] Ni3Ti 11 (111 }Ni local growth direction (1120) Ni3Ti n (110) Ni These relationships are rationalized on the basis of the crystallography of the constituent phases. In recent years researchers in several laboratories have shown that an aligned or "controlled" micro-structure can be produced in many binary eutectic alloys by forcing the alloy to solidify unidirectionally in an elongated crucible.'-3 It also has been found that a unique crystallographic relationship often develops between the two phases in such a structure.4, 5 Since a parallel arrangement of phase particles in an alloy should, and, in many cases, does, produce unique and highly anisotropic properties, the alloys so produced are of potential interest in a variety of applications. Studies of these alloys are also of interest at the academic level because they help to improve our basic understanding of the way in which metals solidify. This paper reports the metallographic and crystallographic structure of another of these alloys—that between nickel and Ni3Ti. In a separate paper, hot tensile and stress rupture properties as well as deformation and fracture behavior of the same alloy are discussed.19 EXPERIMENTAL DETAILS AND RESULTS General Characteristics of the Eutectic Reaction. Several small exploratory Ni-Ti melts were made to resolve a conflict in Hansen6 over the eutectic composition. The alloy containing 16.4 at. pct Ti, Fig. 1, appeared metallographically to be closest to the eutectic composition, although small dendritic patches of proeutectic nickel are present. The eutectic morphology is lamellar and appears quite sharp and angular, indicating a strong influence of crystallographic factors upon the microstructure. Some of the eutectic nickel platelets are continuous with the primary phase, whereas in hyper eutectic melts a "halo" of nickel generally surrounded the proeutectic inter-metallic platelets, indicating that nickel is the nucleating phase in this eutectic reaction. Extensive precipitation of Ni3Ti has occurred in the primary nickel phase in a Widmanstatten pattern which makes the dendrites difficult to differentiate from the eutectic mixture. This phenomenon may account for discrepancies among the eutectic compositions reported in the literature. The sloping solvus line bounding the nickel primary solid solution explains the presence of the intermetallic precipitate. Poole and Hume-Rothery7 report that the solubility of titanium in nickel drops from 13.8 at. pct at the eutectic temperature (1304°C) to approximately 9 at. pct at 700°C (Ni3Ti, on the other hand, melts con-gruently and exhibits essentially no solubility for nickel or titanium). Lever rule calculations based upon Poole and Hume-Rothery's phase diagram indicate an increase from 21 vol pct Ni3Ti in the eutectic mixture at the eutectic temperature to 61 pct at room temperature. Selective point count measurements of the volume fraction of eutectic Ni3Ti platelets in the eutectic microstructure yielded a value of 46 i 2 vol pct, which required extensive precipitation of Ni3Ti from the nickel solid solution onto the eutectic intermetallic platelets during cooling from the solidification temperature. Influence of Directional Solidification. Nickel bar and titanium sponge of 99.9 pct purity were induction-melted in zirconia crucibles under argon in the proportion of 13.8 wt pct (16.4 at. pct) Ti to produce 14-lb master heats which were cast into investment molds yielding 5/8-in.-diam pins approximately 10 in. long. These pins were remelted under argon in horizontal zirconia boats and unidirectionally solidified to produce 1/2-in.-sq ingots approximately 44 in. long. Details of the experimental techniques and apparatus are described elsewhere.'

Jan 1, 1970

By R. A. Wattenbarger, H. J. Ramey

The trend in gas well testing has been to rely more on the early-time flow data of drawdown and buildup tests than on stabilized flow tests. The stabilized testing methods often are not adequate for complicated modern gas reservoirs because many of these reservoirs have extremely low permeabilities and the transient flow period of a well test can last for days or weeks. It has become common to augment the flow capacity of gas wells by hydraulically fracturing their producing formations. In deep reservoirs the induced fractures are generally vertical and tend to follow a single plane of weakness. The presence of a vertical fracture at the wellbore complicates the transient flow behavior of a low permeability gas well. The flow is further complicated when turbulence occurs near the wellbore. Russell and Truittl published transient drawdown solutions for vertically-fractured liquid wells. They developed methods of drawdown and buildup testing utilizing these solutions, which were based on numerical simulation. Clark2 applied the basic Russell-Truitt solutions to analyze fractured water injection wells by falloff tests. Field examples were given to substantiate the method of analysis. The Russell-Truitt solutions and well testing methods can be extended to gas well flow. Millheim and Cichowicz3 presented the drawdown equations for *Now with Scientific Software Corp., Denver. ideal gas flow, including the effects of formation damage and turbulence. Two actual field cases were presented, both of which exhibited extensive fractures and turbulent flow. For the pressure range of these well tests, the use of ideal gas equations was acceptable. These field cases were significant in being the first published data showing the occurrence of turbulence in fractured gas wells. We, also, observed such cases in practice. Our purpose here is to extend the theory of fractured gas well testing to the flow of real gases. To determine the effects of wellbore storage and turbulence on well test interpretation, we developed a finite-difference model to simulate well test conditions. Since gas wells usually are widely spaced and have high compressibility, the emphasis has been put on the early transient behavior before the effects of the outer boundary are noticeable at the wellbore. The Mathematical Model The geometry of our mathematical model is similar to that used by Prats.4 The well is centered in a circular uniform reservoir. A vertical fracture of infinite flow capacity penetrates the formation and passes through the wellbore. The wellbore itself is not important. Fig. 1 shows a sketch of the problem. Fig. 2 shows the idealized model. The equation for the flow of real gas in a porous medium with uniform porosity, permeability and thickness is5-7

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 Lloyd B. Underwood

Dr. Gardener, in Chapter 2, has presented a comprehensive state-of-the- art review of site investigations For tunneling. Nearly all of the techniques he discussed will also be required for future site investigations. Therefore, this chapter will be devoted to a few rather new exploration techniques plus ideas for improving some of the present-day methods. In March 1962, the first symposium on "Remote Sensing of Environment" was held at the University of Michigan.l Since that time, four additional symposiums have been held at the same University. Also, the technical Literature has recently included a number of articles on remote sensing techniques. A recent one appeared in the February 1968 issue of Materials Research and Standards.Vt was entitled "Developments in Remote Sensing Applicable to Airborne Engineering Surveys of Soils and Rocks," and was written by Dana C. Parker. Mr. Parker predicts that aerial reconnaissance will someday supplant soil augers, rock drills, surface reconnaissance, and geophysical surveys as the engineer's primary means of obtaining information about soils and rocks. He states, "The engineer wishing to survey a route or a site or to locate rock and soils suitable for construction projects will be able to push some buttons in an airplane and record all the data required for determining the relevant conditions. In a short time after he returns to earth with his rolls of film and charts, he will be able to reduce and analyze the data by partially computerized techniques and to compile a concise and comprehensive engineering report that gives all the relevant information about rocks, soil, water, and vegetation in the area he surveyed. Most important he will feel as confident with his recommendations, derived primarily from image characteristics and spectral power distributions, as his predecessors did with recommendations based on more tangible evidence obtained from drill cores and surface reconnaissance." The airborne sensors for engineering surveys of soils and rocks are those that sample some electromagnetic property of the materials that com- prise the terrain and cover its surface. In addition to cameras, these include

Jan 1, 1970

By S. A. Levy, J. D. Wood, J. F. Libsch

A study of the preparation and characteristics of a sevies of Fe-C-N alloys has been conducted. X-ray, microhardness, and metallographic data from a series of single-phase alloys produced by controlled nitriding of carburized foils are reported. The existence of a, y', and E carbonitride has been confirmed and it has been found that y' is the hardest of these three phases. These results have been used to interpret the structures observed in nitrided steels. ThIS paper represents the second phase of a three-part study concerning combined nitriding and induction hardening. The first part' reports the engineering properties (depth hardness, fatigue, corrosion, and tempering resistance) obtained when seven different steels were subjected to the combined surface hardening treatment. The present paper concerns the nature of a series of single-phase alloys prepared by controlled nitriding of carburized foils. The objective was to simulate the various layers present in the as-nitrided steels. A third paper will report data concerning induction hardening of the foils and will attempt to set forth a mechanism for the high hardness obtained with the combined treatment. Studies of nitriding generally fall into three categories. The first were performed with bars using conventional nitriding procedures, thus yielding a nitrogen gradient and a series of phase layers near the surface.2-6 Such studies were complicated by the presence of the nitrogen gradient, for it was difficult to correlate microhardness and X-ray data with chemical composition. There were always complications due to penetration of the X-ray beam which yielded data influenced by underlying layers. Similar difficulty was experienced in taking hardness readings on a tapered specimen or in isolating various layers by machining. A second group of investigations was primarily concerned with establishment of regions in the Fe-N7,9,10 or the Fe-C-N phase diagram.8 These were performed with powder specimens which were nitrided in am-monia-hydrogen mixtures to produce a series of single-phase specimens. Unfortunately, the powder specimens were not amenable to either microstruc-ture or microhardness study. The third was essentially a compromise of the first two. Bose and Hawkes," using 0.005-in.-thick iron foils, were able to obtain microhardness, microstruc-ture, composition, and X-ray data on Fe-N alloys of eutectoid composition by equilibration in ammonia-hydrogen mixtures at 1290°F. To obtain a better understanding of the nitriding process and the characteristics of the phases in ni-trided plain carbon steels, the present investigation was undertaken. The investigation was patterned after that of Bose and Hawkes with the exception that nitriding was performed at 930°F (below the eutectoid temperature), as in the case of conventional nitriding. In addition to gaining some understanding of the source of high hardness of nitrided and induction-hardened steels, found in a previous study,' this investigation was concerned with the possibility of controlling the phases present in a nitrided case through the use of ammonia-hydrogen mixtures. Knowledge of the properties of each phase and the conditions necessary for its production could make it possible to avoid undesirable surface layers in nitriding. EXPERIMENTAL PROCEDURE Specimen Preparation. A specimen thickness of 0.005 in. was selected to insure that a uniform nitrogen concentration could be obtained in a reasonable length of time by equilibration in an ammonia-hydro-gen atmosphere. The starting material was a vacuum-cast ingot of pure iron, the major impurities of which were: C, 0.003 pct; 0, 0.014 pct; S, 0.004 pct; N, 0.003 pct.* 'Compositions are quoted as weight percent except as noted. The ingot was heated to 1500°F in a nitrogen atmosphere and forged to a slab 0.25 in. thick. The material was then reduced to 0.005 in. by alternately cold rolling and annealing in a nitrogen atmosphere at 1600°F. This material was divided into five groups of specimens which, after carburizing, yielded the following carbon contents: 0.003, 0.28, 0.36, 0.46, and 0.74 pct C. The carburizing was performed by the Leeds and Northrup Research Laboratories, using a controlled "carburizing potential" which yielded a uniform carbon concentration throughout the cross section.

Jan 1, 1970

By E. T. Turkdogan, L. S. Darken, R. J. Fruehan

Further consideration is given to the application of the quadratic formalism to evaluate the thermodynamics of binary metallic solutions from experimental data. The use of the thermodynamic relation, in(r1/r2) dN2= 0, in the evaluation of activity data is discussed. The empirical correlations derived previously for enthalpies and entropies of solutions in Part II are shown to be predicted theoretically for a special case. The applicability of the quadratic formalism to the activity coefficients for binary organic solutions is demonstrated. DARKEN&apos; introduced a quadratic formalism describing the composition dependence of the activity coefficient in the terminal regions of binary metallic solutions. In a subsequent paper (Part II) Turkdogan and Darkeen2 extended this formalism to the enthalpy and excess entropy of binary metallic solutions, and showed that the available data for the activity coefficients and heats of mixing of many solid and liquid binary metallic solutions confirm reasonable applicability of the quadratic formalism. Much variation was noted, however, in the extent of the terminal regions from one system to another, commonly from about 10 to 70 at. pct. For the present purpose, equations derived previously need be given only for one of the terminal regions, e.g. region (I), 0 < N2 < N&apos;2: where subscripts 1 and 2 indicate quantities for components 1 and 2 and superscript ° the values at infinite dilution; other terms are: N = atom fraction, y = activity coefficient, = partial molar enthalpy of solution, ?HM = molar heat of solution, ?Sx = excess partial molar entropy, ?Sx = excess molar entropy. The heat and entropy like terms (constants) el, and S12 are defined in the following expression for the temperature dependence of a12, thus a12 £12 — s12 rnl 2.303RT 2.303 R l J Using this formalism, the thermodynamics of binary systems in the terminal regions may be described over a temperature range of experisental interest in terms of eight quantities: Lº1—Lº2, ?Sx1,?Sxº2 , £12 ,£21,fiai, S12, and S21. In the previous paper, these quantities were evaluated for many solid and liquid binary solutions, and two significant correlations were observed between these thermodynamic quantities pertaining to the terminal regions, thus [10] and [11] Combining Eqs. [9], [l0], and [ll] and rearranging gives a12 -a21 = 1.382R log rº2- 0.08(?S2xº- ?S1xº) [12] Since the second term involving entropies is small and Eqs. 1101 and [ll] are empirical relations, the above equation may be simplified to a12 = 2.74 log rº2 [13] Using the values of a&apos;s and y°&apos;s compiled in Parts I and 11, a12 - a21 is plotted against log(rº2/rº1) in Fig. 1; the line drawn has a slope of 2.74. For Hg-K at 300°C, log(yº2 /yº1)= —5.10, not shown in Fig. 1, and from correlation [13], a12 - a21 = -13.97; this is to be compared with -10.76 derived from the activity data (Part II).

Jan 1, 1970

By Richard H. Johnson

White Pine Copper Company, a subsidiary of Copper Range Company located in Michigan&apos;s Upper Peninsula, mines a Precambrian sedimentary deposit containing finely disseminated chalcocite, native cop- per and native silver. Silver occurs predominately in certain strata and presently provides a mill head averaging 0.25 ounces per ton. This technical publication traces the development of silver recovery at White Fine beginning in early 1961. White Pine refined copper contains an excess of silver over and above that required to impart Lake Copper properties. The copper does not require electrolytic refining to meet industry purity requirements, nor is there sufficient silver to justify electrolysis.

Jan 1, 1970

Aspects of the formation, decomposition and acid solubility of zinc ferrite were examined to find potential ways of increasing the recovery of zinc from a calcination process of mineral concentrates. Ferrite can begin to form within 2 hours at 450¦C. while complete reaction can occur after 35 minutes at 700¦C. The nature of the starting materials has a pronounced effect on the rate of formation and below 700¦C. ZnSO4 and Fe2O3 proved to be the least reactive of the materials investigated. It is possible that iron in a mineral admixed h sphalerite can be converted to a relatively inactive form, however, it does not seem possible to prevent zince f formation when iron is in the sphalerite lattice. At the two temperatures examined, 650¦C. and 700¦C, the presence of SO2 in the atmosphere accelerate .e formation of ferrite. Prolonged exposure to such atmospheres, however, caused the ferrite to decompose to ZnSO4 and Fe203. The optimum temperature for decomposition was 650¦C. and it was virtually complete within 2 hours in an atmosphere of 10% SO2 in air. Zinc ferrite was also decomposed by CO at low concentrations, and by heating with limestone at 1000¦C. for at least 2 hours. The solubility of zinc ferrite in acid was influenced by the starting materials used. As both the reaction temperature and the time at temperature increased the acid solubility decreased. The acid solubility was a minimum when the ___i_.. n - I -r~...................c -..... F, fe..i+e --A frn... A01- +^ Z(lo/

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,&apos;&apos; 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 Joseph Moses Botbol

In passing the judgments essential to his trade, the geologist may be assisted by two new methods. These will enable him to (1) arrange the minerals of a selected group of base metal mining districts in the order of their typicalities and (2) compute the degree of mineralogic association between the model so derived and a district external to the model. It must be remembered, of course, that the methods discussed in this article are no more powerful than the structure of the model used and the data available. The geologist who employs these techniques must still exercise his expertise

Jan 1, 1970