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By J. Singh

Recently, a Maryland bank became the overnight owner of a toxic waste site through a foreclosure. The original property owners had operated a crash and garbage business on the site and obtained loans for their business venture through the bank. In 1980, their son purchased the property from his parents with mortgage monies obtained from the bank. Failing to make his loan payments, the son defaulted on the mortgage. The bank foreclosed on the property and eventually purchased the property at a foreclosure sale. Shortly after the bank's purchase of the site, toxic wastes were found on the property--the result of disposing solid wastes on the site for 10 years. The bank declined responsibility for contaminating the site and consequently for its cleanup. The Environmental Protection Agency (EPA) took corrective actions to clean up the site. EPA then handed the bill to the bank, citing the Comprehensive Environmental Response Compensation and Liability Act (CERCLA) of 1980 (more commonly known as "Superfund"). CERCLA imposes liability on the current owners and operators of hazardous waste sites.

Jan 1, 1988

By Louis C. Srichta

The rapid depletion of known high-grade ore deposits of the Tri-State district and the recognized need for development of additional reserves, together with increased interest in open-pit mining of low-grade zinc-lead ores led to Bureau of Mines examination of several abandoned mining areas for possible deposits adapted to strip mining. Examination of the North Empire tract in Cherokee County, suggested that mineralized zones contiguous to previously mined 2e deposits presented probabilities of meeting the requirements for an open-pit mine - hence the tract was selected for further investigation by churn drilling. The zinc-lead deposit on the property is in a sink-hole structure that has been subjected to intense deformation and silicification. Numerous shafts, mine dumps, and surface caves are evidences of exploitation of an extensive area. The reported active mining period was 1895 to 1905. No production records are available, but it is generally stated locally that the value of the mill products exceeded $2,000,000 which represents considerable production, considering the low metal prices of that epoch.

Jan 1, 1950

TO metallurgists generally, Arthur S. Dwight is no stranger even to those who do not know him personally. He is one of those contributors to technical progress whose names will go down to posterity because of their being attached to a successful machine or process, such as Dorr, Hardinge, or Marcy, or Wedge, MacDougall, or Herreshoff. The roasting and sintering method and equipment developed by Colonel Dwight and his associate, the late Richard L. Lloyd, may be found in lead smelters throughout the world, and also in many metallurgical works dealing with other ores, including those of iron. It is ordinarily used to desulphurize and agglomerate fine ores for subsequent smelting. Colonel Dwight's citation as James Douglas Medalist reads: "For his contributions to the art of smelting nonferrous ores; and particularly for his pioneer work in developing equipment and technique for sintering such ores and metallurgical products." The medal was awarded at the last Annual Meeting of the A.I.M.E. but unfortunately the medalist was unable to leave Florida at the time to receive it in person.

Jan 1, 1942

By Michael J. Cruickshank

The University of Hawaii, Ocean Basins Division (OBD) shares, equally with the University of Mississippi, Continental Shelf Division (CSD), congressional funding for the Marine Minerals Technology Center, a Generic Minerals Center under the U.S. Department of the Interior's Mineral Institutes Program. The State of Hawaii supports the program by the provision of salaries for the Executive and Technical Directors and by the provision of fiscal, administrative, and facilities support through the Hawaii Natural Energy Institute, the Research Corporation of the University of Hawaii, and the School of Ocean and Earth Science and Technology. The Center's program of research, technology development and education is multi-disciplinary and international in scope. Activities since the MMTC/OBD was established in June 1988 have included: Research projects * Development of a Free-Fall Seafloor Hard Substrate Corer. * The Microtopography of Manganese Crust deposits. * Evaluation of the Cobalt Crust Continuum on Seamounts in the Hawaiian Exclusive Economic Zone. * Graphite Furnace Atomic Absorption Spectrometer. * Computer Aided Design Methodology for Power, Communication and Strength Umbilicals. * Characterization and Environmental Impact Assessment of Tropical * Reef-derived sands for Beach Replenishment.

Jan 1, 1991

By Jeffrey A. Holcomb

INTRODUCTION The passage of Comprehensive Environmental Response Compensation and Liability Act (CERCLA/Superfund) as well as the Resource Conservation and Recovery Act (RCRA) and state laws, have placed added regulatory pressures on the mining industry. These laws which focus on the regulation of hazardous substances and wastes for the protection of the public health and welfare and the environment, present the potential for tremendous financial impacts and liabilities on existing mine operators and owners and/or potential mine operators/owners. This paper takes a brief look at these laws and presents an environmental audit procedure to identify environmental liabilities prior to mine land transactions. The environmental audit approach presented is an overview of the procedures that could be used to document, evaluate and inventory existing and/or potential environmental concerns. This audit procedure can be applied to developed or undeveloped properties and at active or inactive mining sites. REGULATORY OVERVIEW Mining environmental liabilities have been addressed in RCRA, Superfund, the Clean Air Act (CAA) and the Clean Water Act (CWA). Even though the U.S. Environmental Protection Agency (EPA) has determined that mining wastes will be treated as solid wastes under RCRA and not as hazardous wastes, these wastes could still bring about a great deal of financial liability under Superfund. The catch is if the mine wastes generated contain hazardous substances such as the heavy metals arsenic, beryllium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, thallium, zinc and others as well as cyanide. Thus, it is not only important for a mine operator/owner or a potential mine operator/owner to know if the mine wastes generated are hazardous, but it is important to know if the wastes contain hazardous substances. Following is a brief overview of RCRA and Superfund and their potential implications. RCRA RCRA, which provides the basis for the regulation of solid and hazardous wastes, is applicable to active mining and milling sites. Within RCRA the definition of a hazardous waste is provided. This definition applies to owners and operators of mining and milling sites if the operator has stored, disposed or treated hazardous wastes on-site. If this is the case and if strict process control and waste management activities are not adhered to, environmental liabilities may be associated with the site. Superfund The 1980 Superfund law can be applicable to inactive mining sites or to inactive sections of an active facility. The provisions of Superfund call for the regulation of hazardous wastes and hazardous sub- stances disposal and release not only by the existing owner, but also for any previous owner. This concept of joint and several liability means that one party, as among many, can be held totally responsible for the costs of hazardous waste cleanup (Haller, 1987). Furthermore, liabilities under Superfund have also been applied back to past acts; thus, several mining properties, active or inactive prior to the 1980 Superfund law, are at risk of being placed on the EPA's National Priority List (NPL) for cleanup. Last years amendments to Superfund, known as the Superfund Reauthorization Act of 1986 (SARA), provided some significant developments for the mining industry. The major requirement of the amendments as it pertains to owners or operators of mining sites is that the EPA must revise its present Hazard Ranking System (HRS). This is important be- cause in most cases the primary reason for several mining sites having been included on the NPL was due to the large volume of wastes generated. As is typical at most mining sites, large volumes of low toxicity wastes are generated and the current HRS model prejudices against this. It should be noted that this provision only applies to sites that are not already on the NPL or have not been proposed for inclusion on the list.

Jan 1, 1987

By J. M. Smith, G. P. Willhite, J. S. Dranoff

Heat transfer rates were measured in sandstones with flow of gases perpendicular to the direction of energy transfer. Effective thermal conductivities ker ranged from 0.7 to 1.7 Btu/(br)(ft)(°F). The contribution of the solid phase appeared to be the most important in these consolidated materials, although the thermal conductivity of the gas had some effect. The velocity of the gas through the pores of the sandstones had no influence upon ker up to values of 168 lb/(br) (sq ft) in agreement with data obtained for unconsolidated beds of glass beads. The present results indicated that gas mixing, and hence heat transfer by convection in the pores, is less for perpendicular transfer of energy than when fluid flow and energy transfer are in the same direction. HEAT TRANSFER PERPENDICULAR TO FLUID FLOW IN POROUS ROCKS Heat transfer in porous media with pore sizes in the micron range depends upon the fluid in the pores and the geometry of the solid phase. The best characterized system is a bed of solid spherical particles. Heat transfer in this system has been studied extensive1y (Ref. 8 summarizes the literature up to 1959) when the pores contain stagnant fluid. When the fluid is in motion the directions of flow and energy transfer have an effect on the heat transfer rates, as demonstrated by comparing the work of Willhite, et al l3 for perpendicular flow and that of Kunii and Smith9 for parallel flow of energy and fluid. For perpendicular flow, no increase in effective thermal conductivity ke was noted up to mass velocities G of 77 lb/(hr) (sq ft). In contrast, for parallel flow ke, increased with G in the same range of flow rates. These higher values of ke in the direction of flow also have been observed3,4,10 in beds of larger particles, 0.1- to 0.5-in. diameter. For beds of consolidated materials, such as porous rocks, data are not available for these compar- isons, although Adivarahan1 reported results for the parallel case. Hence the primary objective of this work was to measure ke values for perpendicular flow of fluid and energy in porous rocks. Of interest also was the variation in effective conductivity with fluid velocity. APPARATUS AND PROCEDURE In the experimental method, a constant heat flux was applied to the inner surface of an annular section of the porous rock. By cooling the outer wall, a temperature gradient through the annular sample was established and measured with thermocouples placed within the sample at various radial positions, and at three elevations (A,B.C). The location of the 2-in. O.D., 3.75-in. long sample in the apparatus is shown in Fig. 1. Fluid entered the bottom (1) of the 3-in. I.D. (approximate) steel shell, flowed upwards through the sample and out at the top (3). pressure taps (2,4) were used to check the permeability of the sample. The energy flowed radially from the centrally-located electric heater through the sample and was absorbed in the water-cooled jacket. The samples studied were naturally occurring sandstones from different locations with the properties given in Table 1. These materials are identical with those used by Adivarahan 1 for the parallel flow of energy and fluid. Prior to use they were refluxed with toluene to remove hydrocarbons and leached with distilled water to remove soluble salts. Each sample was visually examined and discarded if large nonhomogeneities, such as cracks or stone particles, were noted. Eight copper-constantan thermocouples were inserted in holes drilled radially into the sample with

By Avnulf Muan, P. V. Riboud

The effect of Cr2O3 on melting relations of iron oxide at oxygen pressures slightly above those prevailing in contact with metallic iron has been determined. Liquidus and solidus temperatures of wüstite are raised by the addition of Cr2O3, from 1385°C for pure iron oxide to 1420°C at the peri-ledie point where wüstite, iron chromite, liquid, and gas coexist in equilibrium under the atmospheric conditions used in the present investigation (CO2/H2 = 1). It has been shown in a previous investigation1 that the liquidus and solidus temperatures of iron oxide are drastically increased by the addition of Cr2O3 under the relatively oxidizing conditions prevailing in air. This is to be expected in view of the easy substitution of cr3+ for Fe3+ in crystalline oxide structures which are stable at high oxygen pressures, as demonstrated for instance by the completeness of the solid solution series Fe2O3-Cr2O3 at high temperatures (>1000°C). The stable phase of iron oxide at oxygen pressures approximating those prevailing when metallic iron is present is wüstite. This phase, although commonly represented by the simplified formula FeO for sake of convenience, in reality has a defect structure in which a part of the iron ions are present as Fe3+. It is to be expected that at least a limited amount of cr3 ions will substitute for Fe in this structure when Cr2O3 is added to wüstite. Depending on the ease of this substitution in comparison with that of cr3 substitution for Fe in iron oxide-Cr2O3 liquids under the same atmos- pheric conditions, the liquidus and solidus temperatures of wüstite may increase or decrease upon addition of Cr2O3. The methods of establishing these melting relations and the results obtained are presented in the following. I) EXPERIMENTAL METHOD 1) General Procedure. The quenching technique was used in this study. Oxide mixtures were heated at chosen constant temperatures in an atmosphere consisting of equal parts of CO2 and H2 until equilibrium was established among gas and condensed phases. The samples were then quenched in mercury to room temperature, and the phases present were determined by microscopic and X-ray investigation. 2) Preparation of the Mixtures. Starting mixtures were prepared by weighing and thoroughly mixing Fe2O3 and Cr2O3, or wüstite and Cr2O3. The Fe2O3 and Cr2O3 used were "Baker Analyzed" reagent grades, whereas wüstite of composition was synthesized by reducing Fe203 at 1325°C in an atmosphere consisting of equal parts of CG andHz. In order to avoid contact with crucibles, the equilibration runs were made with small pellets suspended from thin (-0.004-in.) platinum wires. Mixtures made from FOs and Cr203 were readily pelletized at a pressure of 500 atm in a 9.5-mm die, whereas mixtures made from wüstite and Cr203 when treated identically were too weak for handling. In order to obtain a stronger product, these pellets were sintered by heating for 2 min at -1200°C in the same atmosphere as was subsequently used for the equilibration runs (CG/H2 = 1:1). During the sintering, these pellets were wrapped in thin (0.0004-in.) platinum foil, which was stripped off before the equilibration runs. In order to reduce the time needed for equilibrium to be attained, preliminary equilibration of relatively large pellets of each mixture was carried out at -1200°C for 4 to 12 hr. Smaller pellets

Jan 1, 1964

By R. L. Bruening, L. Navarro, R. M. Izatt, N. E. Izatt, S. R. Izatt

Green chemistry principles will be discussed, and examples will be given of the use of Molecular Recognition Technology (MRT) to selectively separate valuable metals such as rhenium and palladium from various copper refinery feed streams. Recovery of these metals has numerous advantages including (i) conservation of valuable resources, (ii) prevention of environmental damage, and (iii) elimination of capital and operating expenses due to re-processing or disposal of metal-bearing streams. INTRODUCTION Refining of copper ores has a long and successful story. The history of copper, one of the first metals mined in human history, illustrates the global challenges faced as a result of increased demand for major metals and for by-product specialty metals found with them in trace amounts (Izatt et al., 2014). Copper has valuable properties, which have sustained its use over the centuries. It is an ideal material for creation of novel materials. Some desirable properties of copper that have proved valuable in our high-technology society include suitability for alloying with many other metals; ease of joining by soldering and brazing; good combination of mechanical qualities; high resistance to corrosion; suitability for many artistic purposes; and, of great importance in the modern era, efficient and economic use as a conductor of electricity. Copper mining in the U.S.A. began in the late nineteenth century in Montana (Izatt et al., 2014). The estimated total amount of copper mined globally before 1800 is about 5 million tons, four times less than is mined in a single year today (Flanagan, 2018). Production of copper in the U.S.A. has remained fairly constant at about 1,300,000 to 1,400,000 metric tons per annum from 2013 to 2017. Specialty metals such as bismuth, rhenium, molybdenum, and others that have become essential in our 21st century technology, and precious metals such as silver, gold, and the platinum group metals (PGMs) are concentrated by geochemical processes in trace amounts in copper ores. These specialty and precious metals were discarded into tailings in early mining operations, since limited extractive technologies existed and uses for most of them were limited. Thus, economic benefits for recovering them were limited, primarily, to silver and gold. Today, copper processing is the main, and often the only, commercial source for certain of these elements (Izatt et al., 2014). For example, molybdenite (MoS2) is the predominant ore mineral of molybdenum mining (Pohl, 2011). Cu-Mo-Au porphyry ore deposits supply ~75% of the world’s copper, 50% of the molybdenum, nearly all of the rhenium, and 20% of the gold. Typical ore grades are 0.5–1.5% copper, 0.01–0.04% molybdenum, and <1.5 g/ton gold. Molybdenite is the primary source for rhenium, among the rarest of metals, which is an essential component of super alloys, such as turbine blades in the aerospace industry (Pohl, 2011). Most rhenium is obtained as a by-product of molybdenite from copper mines in Chile. The case of rhenium raises an important issue. Continued availability of rhenium, selectively concentrated in copper ores, depends on continued mining and processing of copper. Since the mining company’s main interest is typically in copper production, continued recovery of rhenium and other specialty elements present in the ore body is at risk. Dependence of specialty metal supply on continued mining of major metals exists in several additional cases including indium, gallium, selenium, tellurium, germanium and bismuth (Pohl, 2011). PGMs, on the other hand, are typically mined for their own value, which far exceeds that of associated base metals. However, copper ores often contain marketable amounts of platinum and palladium, making their separation of interest, if this can be done economically.

Jan 1, 2019

By Dale R. Ralston, Roy E. Williams, Gerry V. Winter, George L. Bloomsburg

Ground water inflow into a mine and the re¬sultant impact on district hydrology can be pre¬dicted on a site specific basis once the ground water flow systems at the site are sufficiently well under¬stood so that a valid conceptual model can be de¬veloped. Ground water flow systems are controlled by the hydrogeologic properties of the materials at the, site, including hydraulic continuity along flow paths, and boundary conditions. Preliminary delin¬eation of hydrostratigraphic units for conceptual models frequently can be based on surface water data; specifically, spring locations and the gain-loss reaches of streams. Quantitative predictions of mine water inflow and its impact on regional hydrology require col¬lection and analysis of numerous types of data. Hydraulic conductivity must be defined quantita¬tively both parallel and perpendicular to bedding as well as areally for each hydrostratigraphic unit. The characteristics of the Davis shale in case his¬tory number 2 illustrate this concept very well. The storage characteristics also must be determined for each hydrostratigraphic unit and the potential or hydrostatic head should be quantified vertically and areally for each unit. The potentiometric measure¬ments in the Bonneterre Formation as discussed in case history number 2 illustrate this point. The data collection and data analysis techniques constitute the weak link in the analysis of mine inflow and district impact. The technology for char¬acterizing a mine site in the field has lagged behind the technology for mathematical simulation; we at¬tribute this development to the fact that computer modeling is relatively inexpensive compared to field data collection and analysis. On-site tests provide the best means of quan¬tifying hydraulic conductivity parallel to bedding and the storage characteristics of the unit. Pump tests with multiple observation wells provide the best information from on site tests. Hydrogeologie boundaries can be located from such multiple well tests. Multiport piezometers provide a means for determining the vertical potential in a single borehole. Borehole geophysics can facilitate the def¬inition of hydrostratigraphic units. Vertical hy¬draulic conductivity is difficult but not impossible to quantify with existing field test methods; labo¬ratory tests of cores fail to give a value represent¬ative of the field situation. The storage characteristics of a confined (artesian) hydro¬stratigraphic unit can be difficult to quantify when pumping changes the confined unit to an uncon¬fined (water table) case after depressurization and dewatering. Transmissivity and storage coefficient can be approximated to some extent for given field con¬ditions by computer modeling if enough is known about hydrogeologic boundaries. Modeling can be used in a trial-and-error approach to match transmissivity and storage coefficients to existing water level data corresponding to estimated discharge rates. A solution can also be obtained using a tech¬nique referred to as the inverse method. Unfortu¬nately, such a solution is seldom unique. Fracture flow models exist but practicality usu¬ally necessitates reversion to a basic Darcy flow model. Data requirements for fracture flow models could be difficult to fulfill where fracture aperture, spacing, orientation, and length are required. Ob¬taining such data at depth prior to mining would be impossible for any mine simulation in fractured media. We are of the opinion that most fractured media simulations can be accomplished using con¬ventional Darcy flow models by viewing the field problem on a macroscopic scale. The real challenge is to delineate hydrostratigraphic units properly in the field. The question of whether a broken-up fault zone is an aquifer or a barrier boundary is seldom simple. The fractures usually can be treated as an equivalent porous medium in either case. Only a few techniques exist for predicting un¬derground mine water inflow. These techniques fre¬quently are designed to evaluate shaft or tunnel inflow under steady-state head conditions in a sin¬gle layer rather than in multiple hydrostratigraphic units. Few computer programs exist that have the

Jan 1, 1986

By Peter A. Allen

INTRODUCTION Lac Minerals Ltd., a significant North American producer of gold and other metals for over three decades, recently completed the financing for its third discovery in an eight year period. From 1975 to 1982, three important gold deposits in Quebec and Ontario: namely Bousquet, Doyon and Hemlo, were located and tested by company geologists. When current development plans are complete, Lac will have injected $400 million into these deposits. A discussion of these projects and their financing reveals some extraordinary challenges faced by top mining management. Responses to these challenges developed by Lac management may interest executives planning to proceed with new North American gold or base metal mines. MINE DE BOUSQUET In 1976, we explored a property containing a large low grade surface gold deposit. The geologial setting was exciting and we tested recent rethinking about the volcanigenic genesis of gold and base metal occurrences. These ideas helped pus to persist in drilling a nearby conductor and 600,000 ton, 0.22 ounce/ton orebody was outlined. With gold at $Cdn.150 per ounce the feasibility was approved and work started February 1978. Availability of a company custom mill 35 miles away reduced our immediate capital needs to $8.5 million. First of all, understanding the geological significance of results at Bousquet was critical. Mine and surface exploration geologists at Lac are continually and closely working together to better understand the nature of gold deposits in the Shield. This management emphasis on both pure and mine geology meant that a much larger ore reserve could confidently be predicted. (A proposal to quickly develop and ship the ore to a nearby company mine was discarded.) Instead of designing just for the initial plan of 500 tons per day we therefore included headframe, shaft and hoisting capacity for 1,700 tons and provided a compartment for future shaft deepening. These prebuilt additions were welcomed within two years. The type of collaboration whereby surface and mine geologists make study and field projects of each other&apos;s problems sets the foundation for this predictive ability. At Lac, the traditional responsibility for and supervision of the mine geologist by the mine manager is modified by this collaboration. This adds interest and scope to the geologist&apos;s work and lets him think beyond production requirements. Besides such management considerations, dedicated, professional geologists with integrity and lots of practical experience are needed to plan successful developments like Bousquet. Second, projecting future bullion revenue was critical and our experience selling production for future delivery gave us a way to ensure that loan repayment at term would not be jeopardized by falling metal prices. Output from a single mine is often reduced or curtailed for numerous reasons, so "selling forward" is done best and with least risk by companies like Lac with more than one or two producing locations for that metal. At first, a forward marketing program was considered unwise, speculative and unorthodox by analysts and other producers. Declining markets in the early 1980s prolonged gold project capital recoveries however, and critics were better able to appreciate the usefulness of such a tool. The notion that gold miners shouldn&apos;t sell forward is rooted in the belief that long-run gold prices will rise as modern social theory implementation in democracies inevitably erodes currency values. Selling against this trend goes against this industry belief or "ethic" and is at odds with the company shareholder who expects the gold price to rise not fall. Nonetheless, an efficient tool is available to the gold producer (not to most other metal producers) to quickly disengage from adverse price trends or to lock in spot prices instantaneously for two years or more of profits. Gold had recently retreated from U.S.$200 to $104 and now had reversed to $150. Lac had been forced to close several of its producers during the late 1960s because central bank-controlled

Jan 1, 1985

By J. D. Patsey, G. T. Lineberry

Introduction A computer program was developed for analyzing drum-type hoists before modifying an existing system or designing a new one. Its use permits the preliminary evaluation of a system before seeking technical assistance from mine hoist designers and manufacturers. The user-friendly program accepts a variety of data and analyzes hoisting systems for any balance state. The program can be used to calculate skip capacity to yield a desired production rate, solve for drum face width, select a permissible wire rope, estimate total horsepower of the hoist plant, and estimate annual power cost. Whether required for a large mining complex or for a relatively small operation, a hoisting system must be carefully designed to ensure the efficient, reliable, and safe flow of material. Because shaft sinking and hoist installation can total between 2.5% and 3% of the cost of opening a deep mine, proper hoist selection is critical. Today&apos;s mining engineer has at his disposal the most powerful design and analytical aid ever, the micro- computer. There is, unfortunately, limited software for the study of hoisting systems, unlike that for other materials handling equipment (Manula and Albert, 1980; Prelaz et al., 1964; Bucklen, 1969; Thompson, 1985). HOIST reduces a time-consuming set of calculations to a concise package of interrelated subprograms. A literature review revealed no common-user pro- grams to analyze hoisting systems, although at least four major hoist designers/manufacturers/installers have their own in-house programs. To provide a tool with which the mining engineer could preliminarily analyze a materials hoisting system or could check the calculations of a hoist contractor, a computer program was developed. HOIST was written in BASIC for the IBM-PC for ease of program adaptation and to en- courage field use on compatible systems. Details of program development are omitted, since the basic principles of hoisting analyses are relatively straightforward, simple, and readily accepted (Har- mon, 1973; Nordberg, n.d.; Adler, 1957). Program features, intended usage, and benefits of the com- puterized solution are emphasized over theory development and mathematical rigor. Background The mine hoist system that is selected and installed at a mine is the "lifeline" of that mine, with installations lasting 20 years or more. Thorough study is warranted to ensure that productivity demands are met at a minimum cost per ton. The increased cost of a large, powerful, high-speed hoist must be offset by increased production to justify its selection. To optimize this tradeoff, an extensive hoisting analysis should be performed. The analyses to properly size the skip (or cage ) , the drum, and the hoist drive are conducive to computerization, permitting rapid evaluation of changeable operating and design parameters, such as velocity, acceleration, state of balance, and productivity demand. The program is particularly useful in conducting sensitivity trials, such as investigation into the effect of change of productivity on skip capacity and on horsepower of the hoist drive. HOIST is currently limited to the study of drum-type hoists with cylindrical drum(s). However, only minor changes to the program would permit analysis of friction hoists and conical drum configurations. Model development and testing The program is based on accepted equations and physical relationships. Examples of manual calculations formed the basis for decision points and program branching. Data is input in the order that it would be needed if the problems were solved manually. The choices are arranged likewise. HOIST was developed in sections, with manual solutions performed to check program logic. The testing became more rigorous as sections were completed. Output from one section becomes input for following sections, as appropriate. The simplified flow diagram of HOIST is given in Fig. 1.

Jan 1, 1988

By William L. Langdon

PRELIMINARY COMMENTS Recent years have been difficult for the mining industry, as reported in the most recently published Minerals Yearbook (Volume III), the estimated value of world crude mineral production has been generally declining since an historical peak in 1979 (16).* The costs of mineral extraction have, however, been rising rapidly. Individual project costs are, in general, exceeding the growth rate of mining companies, while operating and technical risks continue to increase (16). Risks resulting from currency flotation and political actions in the host country are also on the increase. Labor difficulties (such as those experienced by Phelps Dodge) and the Reagan Administration&apos;s recent rejection of a proposal by the International Trade Commission for higher tariffs and/or quotas on copper imports have also contributed to the mining industry&apos;s difficulties. The net result of these factors has been financial difficulties for mining companies with respect to paying for their current financial obligations as well as trouble finding new financing. It may be that one of the main factors in determining the future of the mining industry will be centered upon capital structure, i.e. how its assets are financed. Historical Perspective on Capital Structure In The Mining Industry As discussed by Isreal Borenstein in (4) and Thomas Navin in (7), mining firms typically have used a financial model based upon high financial leverage, i.e. large amounts of debt relative to equity. This has been especially true for American firms developing orebodies discovered overseas. Problems sometimes occurred for those who were forced to commit themselves to completion guarantees in order to obtain bank loans. Mines under these circumstances must be brought into operation regardless of market conditions. Politicians in overseas countries also may use the high profits required by these high risk ventures to argue for nationalization of mines. Coupled with the frequent use of high leverage, mining companies traditionally have paid out a higher percentage of earnings in the form of dividends than manufacturing firms. This is significant, in that such funds paid out in dividends are not available for other uses. Hence, a greater reliance upon debt and/or additional stock issues than would ordinarily be the case for manufacturing firms. Thomas Navin has stated in (7), that the theory behind the high dividend payout was that, "most mining investors thought of themselves as investing in a wasting asset, one that would gradually deplete over time until it ultimately became valueless." Investors, therefore, required a receipt, in the form of dividends, of a percentage of current earnings and a return on original capital. This view of reality, apparently, has not changed in some quarters, even though modern mine management ordinarily replaces depleted mines with new ones. It may be that this practice of high dividend payout coupled with relatively high financial leverage should be reexamined. Current capital structure theory could prove interesting and useful for those concerned with current conditions. Capital structure patterns and related practices in this industry are not, in many cases, congruent with those thought by some to be theoretically optimal. Prelude to Capital Structure Discussion With a few notable exceptions (such as the Guggenheims and Anaconda&apos;s chief operating,. officer in 1971) mining companies&apos; chief executives and boards of directors have not been persons with financial backgrounds. This, one could conjecture, might have accounted for the relatively nonsophisticated nature of capital structures of mining companies. In order to appreciate the possibilities with respect to alternative influence on a firm&apos;s performance, one must be acquainted with the basics of financial theory. This paper is an attempt to familiarize the reader with (1) capital structure in general, (2) the usual components of this structure, (3) the general theory behind the use of financial leverage, and

Jan 1, 1985

By S. C. Miller, R. D. Carter, H. G. Riley

A merhod based on theoretical considerations is presented for estimating srabilized performance of gas wells from data obtained from short-term flow tests. Calculated results are presented for II gas wells evaluated with four-to five-hour flow tests. For seven wells on which comparison war available, satisfactory agreement between measured and calculated performance was obfained. Although the final results are favorable, diflerences in flow capacity k,h obtained from flow tests conducted at different rates were observed. This inconsistency did not seriously affect the calculated results in the test wells. INTRODUCTION In order to negotiate the sale of gas from newly drilled gas wells and to plan otherwise for the orderly exploitation of gas reserves, it is necessary to predict the long-term withdrawal rates physically possible for each well. Since low permeability gas wells do not stabilize except after a lengthy period of flow, the operator is unable, without wasting large amounts of gas, to measure directly the stabilized performance prior to contracting for sale of the gas and connecting the well to a pipeline. This problem is not new, but is one which has recently received considerable attention because of the rising importance of natural gas in the economy and new emphasis on the development of gas reserves. Thus, a method is needed for estimating stabilized performance from information obtained from short-flow tests in which stabilized flow is not attained. Such short tests would be suitable for wells not connected to a pipeline since the tests require only small amounts of time, labor and production of gas. Other requirements of such a method are short calculation time and use of a model of the gas well and its reservoir drainage area which is as consistent as possible with present theoretical, experimental and field knowledge. The method presented herein was developed in an effort to meet these requirements. It has been named the "two-Row method". In addition to the section on the evelopment and description of the method, a description of field application of the method and a discussion of well test results are in- cluded. Finally, there is a section on an additional consideration prompted by some of the test results. The Appendix contains certain details of the derivation of the two-flow method and a sample calculation for Test Well 1. MATHEMATICAL DEVELOPMENT AND DESCRIPTION OF THE METHOD The method is based upon the following assumptions: (1) The system can be described as a finite cylindrical gas reservoir produced by a single cylindrical well located at the center of the reservoir. Flow is strictly radial. (2) Flow obeys Darcy&apos;s law except very near the well where a quadratic flow law is assumed. (3) The system is also characterized by a laminar flow skin factor. The use of a quadratic or turbulent flow term is more fully justified in Refs. 1 and 2. When such a system is opened at the wellbore to constant rate flow from an initial condition of uniform pressure distribution, the radius or drainage quickly passes through the non-Darcy flow and "skin effect" region imrnediately surrounding the well. After the drainage radius or "transient" has passed beyond this region and before it reaches the external boundary, drawdown can be expressed by&apos;." After the drainage radius reaches the external boundary, stabilized flow exists and drawdown is given by&apos;," Eqs. 1 and 2 form the basis for the method. The validity of these equations will now be examined in the light of some well test data previously available. It has been found by actual measurements on gas wells that the relationship between drawdown and flow rate, that is the performance curve, is closely approximated by&apos; Eq. 3 is a straight line on log-log graph paper. Eq. 2 and, for any lixed value of time, Eq. 1 plot as a curve which is slightly concave upward on log-log graph

By R. F. Holub, E. Franco, T. B. Borak, K. J. Schiager

INTRODUCTION According to a recent analysis by Schiager et al.(1981), inhalation of radon daughters continues to contribute the largest risk from exposure to radioactive materials in underground uranium mines. The American National Standards Institute (1973) has published a concensus standard for radiation protection in uranium mines. According to this standard, a monitoring system for radon daughters must be capable of measuring the annual accumulated exposure in working level months within an uncertainty interval of 50% at the 95% confidence level. To satisfy this criterion, uranium mining companies in the USA have adopted a procedure consisting of single or periodic measurements of the air concentration of radon daughters. All of the measurement methods sample a known volume of air through a filter. After a specified delay interval, the filter is analyzed for radioactivity. The exposure rate from total airborne potential alpha energy in units of working level (WL) is estimated from the measured activity on the filter. For control purposes, this measurement establishes whether or not a work area is safe for occupancy by miners. For routine dosimetry, the concentration estimated from the grab sample is assigned to the appropriate work area. It is then assumed that the concentration of radon progeny is equal to the average of the two measurements at the beginning and end of the specified interval. Meanwhile, the work locations and exposure times of each miner are recorded on the daily time card and verified by the shift supervisor. Most cards provide space for 15-minute time intervals. The exposure in working-level hours (WL-hr) for each shift is obtained by summing the time spent in a given location multiplied by the exposure rate (WL) assigned to that location.The exposure of an individual miner to radon progeny is summarized on a weekly basis and commonly reviewed each month. These values are then accumulated in units of working level- months (WLM) during the calendar year. EVALUATION TECHNIQUE AND RESULTS The evaluation of grab sampling methods for monitoring exposure to radon progeny is presented in two sections. The first section examines each method individually according to accuracy, precision, and uncertainties attributed to human errors. The second section includes an analysis of procedures which are common to all measurement methods. The ultimate goal is to determine whether a specific measurement method, or grab sampling in general, can fulfill the criterion that the annual accumulated exposure of each miner be known to within ± 50% at the 95% confidence level. In addition it is essential that the above criterion be satisfied at an acceptable cost to the mining company. The results of each testing procedure are presented in terms of the contribution of the relative uncertainty in the estimates of cumulative WLM. Each of these are then combined to form a figure of merit for the complete monitoring system. The method of combining statistical uncertainties and interpretation of the results is subject to some debate. However, since all of the tested parameters enter into the final computation of WLM multiplicatively, we have used the commonly accepted procedure of combining the squares of the relative uncertainties. We have also assumed that each of the uncertainties is derived from independent random variables and the covariance of any two variables is zero. A description of each grab sampling measuring method is given in Table 1. Also included is the equation used to compute WL from the measured quantities. Accuracy (U A) Our definition of accuracy is based on the uncertainty inherent in any method which attempts to estimate potential alpha energy without unambiguously determining the concentration of the three unknown radioisotopes, RaA, RaB and RaC. (For simplicity, the RaC and RaC&apos; nuclides are referred to in combination as RaC.) The inherent uncertainty strongly depends on the mixture of these three components at the time of measurement.

Jan 1, 1981

By R. M. Asimow

Both smith1 and wells2 have shown that the dif-fusivity of carbon in austenite increases rapidly with increasing carbon concentration. Smith has shown, in addition, that part but not all of this increase can be attributed to the concentration dependence of the activity coefficient of carbon in austenite. From the work of Eshelby&apos;, it is known that, because of the image displacements, there is a uniform dilatation of the material in a body containing random centers of dilatation. It is thus tempting to explain the enhanced diffusivity as resulting from this apparent negative pressure caused by the interstitial carbon atoms.* That is, the activation free energy for diffusion is not directly a function of concentration if we consider that the alloy is subjected to a concentration-dependent pressure. To proceed with a quantitative solution, it is necessary to determine the activation volume AV for the diffusion process. An exact calculation of AV is quite a difficult problem and does not appear to have been solved as yet. A simpler procedure is to use the semiempirical, macroscopic theory of seyes&apos; which relates the activation free energy AG to AV. Keyes has shown that for many types of diffusion processes the following relationship is valid Where p is the Gruneisen constant and x the compressibility. This relationship is based on the assumption that AG can be identified with strain-energy terms. In general there will also be contributions to AG due to a change in the energy of the valence electrons of the metal; thus the relation must be considered largely empirical. Surprisingly, for self-diffusion where it is well-known that the electronic contribution is quite important,&apos; the Keyes relation works quite well for many systems. For interstitial diffusion where it might be expected that the relationship is on a firmer theoretical basis, the limited experimental data available is not in particularly good agreement as can be seen from Table I. However, it must be remembered that besides the uncertain basis of the Keyes formula there is considerable uncertainty in some of the experimental values of AV. The only real justification for using the Keyes formula in the present analysis is that it gives a result which satisfactorily solves the problem at hand and, further, there are no more reliable procedures for calculating AV available. The coefficient 3 in Eq. [I] is determined such that the room-temperature value for x is to be used. The activation entropy AS is estimated as 8.95 x 10"3 kcal per OK mole using the values in Table I1 and the Zener" relation AS = PAHIT, where p is a dimensionless thermal coefficient of Young&apos;s modulus which is to be evaluated at low values of T/T,, aH is the activation enthalpy, and T, is the melting temperature of the alloy. The resulting value of AG at 1000°C is 25.6 kcal per mole. The Gruneisen constant (p = 3cup/XC,), where p is the density, is evaluated from the room-temperature data in Table I1 after calculating C, from the relation. A value of p = 8.32 g per cu cm based on the value of a. in Table I is used. The result is C, = 5.0 x lo6 erg per g, H = 2.32, and AV = 3.41 cu cm per mole at 1000°C and infinite carbon dilution. It is assumed that the activation volume is not a function of carbon concentration. The theory could be refined to consider AV a function of concentration, but due to the uncertainties in the parameters there seems little justification for this. Carbon dissolved in austenite forms a nonideal solid solution, so that in writing an equation for. the diffusivity of carbon it is necessary to take into account the change in activity coefficient with concentration. The resulting equation is16

Jan 1, 1964

By J. J. Gilman

RECENT experiments have shown that the mar-tensite reaction in a standard tool steel is influenced by the history of the reacting austenite. The martensite reaction proceeds to a given extent at a higher temperature in austenite formed from an annealed spheroidal structure than it does in austenite formed from tempered martensite: that is to say, a prequench lowers the temperature range of the martensite reaction in this steel. Furthermore, a prequench alters the appearance of the martensite as compared to martensite formed from "virgin" austenite. The steel used for this work was a manganese nondeforming tool steel of the following composition: C, 0.85 pct; Mn, 1.43; Si, 0.23; Ni, 0.12; Cr, 0.59; and W, 0.59. A piece from a rolled bar was forged to Vz in. sq and annealed to a spheroidal structure. Disks 1/8 in. thick were used in the experiments. Several sets of the specimens were prepared and austenitized in lead at 1475°F. Three sets were held at 1475°F for 15 min, quenched in water, and immediately reheated to 1475°F. After this quench the three sets were held for 5 min, 30 min, and 3 hr, respectively, at 1475°F and then the individual specimens in each set were quenched in molten baths to 325", 300°, and 275ºF, respectively, and held for 15 sec. Immediately after the quenching treatments? the specimens were tempered at 600°F for 30 sec to darken the martensite and then were quenched in water. The holding times were short enough to avoid isothermal transformation. Three other sets of specimens were given the same final quenching treatments as the first three, but they were austenitized at 1475°F for 20 min, 35 min, and 3 hr and 15 min, respectively, without an intermediate water quench. The two individual specimens from each set were quenched together in order to eliminate quenching errors. Several experiments were run in this way but only the six sets referred to are described in detail because they all yielded essentially the same results. By means of the stated heat treatments the martensite reaction was investigated for: 1—austenite formed from an annealed structure, and 2— austenite formed from tempered martensite. The martensite reactions of the two types of austenite differed significantly. This is shown by Figs. 1 and 2. Comparison of the photographs on the left in Figs. 1 and 2 with those on the right shows that less martensite was formed by a quench to a given temperature from prequenched austenite than from austenite formed from an annealed structure, that is, the prequench suppressed the martensite reaction. The effect was observed for specimens austenitized 20 min, 35 min, and 3 hr and 15 min. A comparison of Figs. 1 and 2 shows that the martensite reactions in both sets of specimens occurred at lower temperatures with increased austenitization time. This was caused by the increased dissolution of residual carbides with time at 1475°F. However, the difference in amount of martensite formed in prequenched austenite as compared to virgin austenite was approximately the same for all three austenitization times. One further observation should be noted. The needles of the martensite formed from virgin austenite are somewhat longer on the average and show less of a tendency to cluster than those of martensite formed from prequenched austenite. This causes the martensite on the right in Figs. 1 and 2 to have a more acicular appearance than the martensite on the left. Since the sets of specimens used in this work were austenitized for identical total lengths of time and the effect of a prequench on the martensite reaction existed for specimens held at the austenitizing tem-

Jan 1, 1953

By Richard J. Waxweiler, Frank E. Lundin, Robert J. Roscoe, Victor E. Archer, Michael J. Thun, Joseph K. Wagoner

[Introduction] Since excess lung cancer mortality was first noted in the late 1800&apos;s among Joachimsthal-Schneeberg miners, there have been a number of studies of the long term health effects among various types of miners exposed to elevated levels of radon and its radioactive decay daughters. Substantial excesses of lung cancer have been noted among miners in the Joachimsthal mines (Sevc, 1976) , lead-zinc miners in Sweden (Axelson, 1979) , fluorspar miners in Canada (DeVilliers, 1971) , iron miners in Sweden (Renard, 1974) , uranium miners in Canada (Hewitt, 1976), and metal (Wagoner, 1963) and uranium miners in the United States (Lundin, 1971; Archer, 1976). The latter prospective cohort has also been shown to be at an excess risk of death due to tuberculosis, nonmalignant respiratory disease, and accidents when followed through September 30, 1974 (Archer, 1976). This report extends the followup of this cohort of miners through December 31, 1977 and expands the mortality analysis to investigate more cause-specific categories. [Methods] During the decade beginning with July, 1950, medical teams from the United States Public Health Service (USPHS) examined 3362 white and approximately 780 nonwhite males who had worked underground in uranium mines in the Colorado Plateau at least one month by January 1, 1964. Occupational, medical, and smoking histories were obtained during the examinations and often updated/confirmed during subsequent annual censuses of the miners conducted by the USPHS. The white miners now have been followed-up through December 31, 1977 using the Social Security Administration, Internal Revenue Service, direct telephoning and various other sources. Death certificates were obtained for the deceased and coded directly into the Seventh Revision of the International Classification of Diseases, Adapted, using the rules in effect at the time of death. Deceased miners for whom no certificate has yet been located were assumed dead on the date specified by the reporting agency, cause of death unknown. The uranium miners cohort was analyzed using a modified life-table system developed by the National Institute for Occupational Safety and Health (NIOSH). Person-years at risk of dying (PYAR) were calculated for each miner from his first USPHS medical examination date or date upon completion of one month of underground uranium mining if that was later. PYAR were calculated specific for five-year age groups, calendar periods, and periods after first underground uranium mining. The numbers of cause-specific observed deaths among the cohort occurring by December 31, 1977 were compared to the numbers of expected deaths. The expected deaths were calculated by multiplying the appropriate PYAR by the United States death rates for white males specific for five-year age groups, five-year calendar periods, and cause. The results were summed over the age and calendar period specific categories to obtain the total expected deaths for each cause. Standardized Mortality Ratios (SMR&apos;s) were calculated for each cause by dividing the observed number of deaths by the expected number of deaths and multiplying by 100. In some tables, two-sided 95% confidence intervals for the SMR&apos;s were computed using either Fisher exact confidence limits, if the observed frequency was less than eight, or approximate confidence limits, if the observed frequency was eight or greater, to indicate statistical significance. Because a priori hypotheses had been well established, one-sided lower confidence limits were used for tuberculosis, lung cancer, other nonmalignant respiratory disease (ONMRD), accidents, and total mortality. [Results] The cohort included 589 miners first examined in either 1950, 1951 or 1953; 753 first examined in 1954; 1235 first examined in 1957; 5 first examined in 1958; and 782 first examined in 1960. In Figure 1 the distribution of the cohort by first year of underground uranium mining indicates that 13.7% started before 1947 and would have thus had an opportunity to be followed beyond 30 years

Jan 1, 1981

By R. G. Schaal

The Magma Mine at Superior, Arizona had an unimpressive beginning as a. worked out silver mine that was purchased in 1910 for $130,000 and then incorporated into the Magma Copper Company which has been continuously mining the deposit since 1915. Copper is the principal metal produced. However, zinc, gold, silver and iron have also contributed to the total metal product. Prior to 1973, the production rate of 1500 tons per day was maintained by hoisting 4 and 5 ton pay-loads at speeds up to 1100 FPM through four small hoisting shafts. The hoists used included 8&apos; and 7&apos; diameter double drum, double clutched doc. and a.c. motor driven geared units built as early as 1917. One old timer that did yoeman&apos;s service for many years was an 8&apos; Bollen Pulley with a.c. geared drive that utilized an endless rope system with mechanical grip and release mechanism built into the pulley&apos;s throat. Primary power for all of these old production hoists was 25 Hertz. Exploration that was completed in 1967 developed a reserve of 10 Million tons of 5 per cent copper which was sufficient to justify new capital expenditures for enlargement of productive facilities to 3300 tons per day. To reach the new reserves a 22&apos; I.D. concrete lined vertical shaft was sunk to an initial depth of 48431. A 12 ½ diameter adit was bored from the mill side of the mountain to intercept the shaft at a point about 1100&apos; below the collar. This 9200&apos; long adit provides the right-of-way for the mine to mill railway and egress for heavy supplies from rail head as well as a conduit for potable water, electric power, compressed air and mine drainage. Mine operating levels begin 3582&apos; below collar and thereafter have been cut at 100&apos; vertical intervals. Skip loading stations have been installed 4282&apos; and 46821 below collar with an in-shaft skip dump station located 800&apos; below collar. This provides for 4500 tons of storage above the mine to mill train loading station located 1100&apos; below collar. Ore and waste are moved horizontally from stope chutes and drift headings by rail haulage to transfer raises which channel all material to the two mentioned skip loading stations. The 22&apos; diameter shaft crossection is arranged with the two skip compartments on the south side separated from the manway and utility compartments by the cage compartment. The cage counterweight operates in a portion of the southwest quadrant of the shaft. The hoisting plant consists of two conventional Nordberg double drum, single clutch, geared, d.c. motor driven units that are identical except for the drives and automatic controls. The drums are 15&apos; diameter x 105" face with LeBus grooving for 2-1/8" diameter wire rope wound in three layers. Mechanical design emp1o::ed is the same as has been used for the past twenty- five years. One drum is attached to the main shaft by 2 large bolted integral shaft flenge. The loose drum is engaged by a 4-arm positive tooth clutch meshing with radially cut teeth of the clutch ring which is bolted to the drum. The drums are one-piece steel plate weldments having a finished weight of 60 tons each and are mounted upon a 36" diameter shaft that also weighs 60 tons. With the addition of brake rings, clutch, bull gear and rope, the total dead weight adds up to nearly 250 tons that is supported by just three double row spherical roller pillow block bearings. There is no bearing between the drums. All pinion shafts as veil as all head sheave journals are supported in the same type of antifriction bearings.

Jan 1, 1975

By Donald L. Johnson

REVIEWS on the applications of optical ellipsometry to the study of polycrystalline metal surfaces and oxidation-corrosion processes have been presented by Kruger and Hayfield, and white.&apos; In view of the ability of this method to measure differences in film thicknesses to below 10A, ellipsometry was used to study nitrogen chromium surface reactions during the early stages of growth. Chromium specimens in the form of a vapor-deposited film on glass substrate were exposed to purified nitrogen for selected time increments at 700°F. This temperature was selected because it gave the best combination of exposure time and thickness change. Ellipsometer readings were taken immediately after exposure to determine polarizer and analyzer angles using monochromatic light at 5000A.2 After each set of readings was obtained, the specimens were exposed for an additional increment of time in nitrogen and a new set of readings taken. Film thickness was computed from LUCy&apos;s3 equation for nonabsorbing thin films. In Lucy&apos;s derivation, two equations for computing thickness were obtained. Peterson and Bashara4 have discussed the validity for using one of these equations when an independent value of the refractive index is used. The film was assumed to be Cr2N (Ref. 5) and was determined to be optically isotropic. Optical isotropy was determined by rotating the films about the surface normal and noting that the azimuth and phase difference did not change. Since Cr2N is reported to be hexagonal, it is assumed that optical isotropy results from randomly oriented grains of very small size. The thickness was computed using refractive indexes varying from 1.6 to 2.0. The maximum variation in computed thickness over this range for a given exposure was 20 pct. The data reported are based on a refractive index of 1.8. Reference readings on the metal surface were taken just prior to nitrogen exposure. No attempt was made to deoxidize or denitride the metal surface after vapor deposition, although specimens were observed to gain approximately 2A per day in air at room temperature. Twelve experimental exposures were made on a single sample over a total accumulative time of 132 min. Additional experiments over longer time intervals were made to determine the effect of heat up and cool down during and after exposure. As a result of these experiments, the thickness computed for each exposure was increased by 4A. Time profiles based on the linear law are similar to the oxidation profiles for many metals.&apos; The rate of accumulation of the nitride film is rapid at first and slows down as the film thickness increases. The parabolic law x2 =k1t +k2 [11 gives a straight line in Fig. 1; therefore, it is concluded that the kinetic behavior is parabolic. Sey-bolt and Haman5 reported similar results for CrlN on chromium at 1000°C although the order of the thickness was much greater (10-3 cm). Analysis of thickness data based on other values of refractive index shows that the curves are shifted vertically but retain the same shape. According to Mott,7 it is expected that for thin films k2 is zero in Eq. [I]. Since the plot in Fig. 1 is linear through the origin, k2 is zero and the parabolic nature of the film growth is further indicated. The parabolic rate constant, calculated from the slope in Fig. 1, is 4.4 x 10-16 sq cm per sec. The corresponding work (+) required to bring an electron from the metal into the oxide is estimated to be 1.5 ev.7 The author thanks professor N. M. Bashara and D. W. Peterson, Electrical Materials Laboratory, University of Nebraska, for making the ellipsometer available and providing technical assistance. The Electrical Materials Laboratory is supported by the office of Naval Research, NONR 3718 (01). This work was partially supported by the Engineering Experiment Station and the Mechanical Engineering Department, University of Nebraska.

Jan 1, 1967

By C. R. Masson, M. L. Pearce

The nitrogen contents of seven specimens of iron and steel were determined by the three methods. Good agreement won generally observed between the results of the isotope -dilution and Kjeldahl determinations, tltzts establishing the reliability of the isotope -dilutzon technique. For some specimens, the vacuum-fusion values at 1650 °C were lower than the corresponding Kjeldahl values by up to 0.0015 pct absolute. These differences were eliminated for a specimen of "pure" iron by performing the vacuum-fusion analyses at 2100 ° to 2240 °C. The reason for this relatively high temperature required m the vaczium-fusion analyses is discussed. ThE determination of nitrogen in iron and steel has been the subject of numerous investigations and a concise review of the extensive literature in this field has recently appeared.&apos; Two methods of analysis are most commonly employed, the vacuum -fusion and the chemical or Kjeldahl method. Except in special cases where the presence of certain alloying elements may present difficulties, both methods are generally regarded as applicable, although the vacuum-fusion method is more sensitive and is often preferred for samples of very low-nitrogen content. The method of isotope dilution, first employed for the determination of gases in metals by Kirshenbaum and Grosse,2 has recently been applied to the determination of nitrogen in iron and steel.3,4 The method is attractive in that it does not require the quantitative extraction of gas from the metal specimen. Staley and Svec3 modified the standard Kjeldahlpro-cedure by introducing, along with the steel sample, a measured amount of ammonium sulfate enriched in the isotope 15N. The nitrogen content was obtained by measuring the isotopic ratio 15N/14N in the resultant solution. The technique involved the distillation of nitrogen as ammonia from alkaline solution and subsequent oxidation of NH4+ in the distillate to gaseous nitrogen. The results for iron and steel samples of commercial origin were often in reasonable agreement with values quoted by the suppliers, although occasional marked discrepancies were observed, particularly with the results of vacuum-fusion analyses. Preliminary work in this laboratory4 on the determination of nitrogen by isotope-dilution in the gas phase yielded results for three samples which were significantly higher than the values obtained by vacuum-fusion. The present paper describes an extension of this work to a wider variety of samples. Analytical results by the Kjeldahl method are also reported. EXPERIMENTAL The technique employed for the isotope-dilution determinations was similar to that described elsewhere.4 Several minor modifications were made to the apparatus. These included the use of molybdenum instead of platinum-rhodium suspending wires when crucibles were degassed at temperatures above 1600°C. The circulatory system used previously for converting CO to CO2 was replaced by a single chamber, the walls of which were cooled directly in liquid nitrogen. Temperatures were measured with an optical pyrometer which had been recently calibrated and, as in the previous study, were minimum values obtained by sighting on the center bottom of the crucible. Temperatures obtained by sighting on the interior walls were always higher by 100&apos; to 130°C with the design of crucible employed. Flat-bottomed crucibles exhibited an even larger temperature difference. To check the efficiency with which crucibles were degassed in the isotope-dilution apparatus, several experiments were done in the vacuum-fusion apparatus, suitably modified4 for isotope-dilution studies. Faster pumping speeds and higher degassing temperatures were possible, the latter due to the use of a generator with a higher power output (10 Kva at 398 kc per sec). In these experiments the combustion of CO was omitted and a correction4 was made for the contribution of CO to the ion current at m/e 28, used in determining the isotopic ratio R = l5NP4N. This correction did not seriously influence the re-

Jan 1, 1962