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By Mark I. Copeland

This study was conducted by the Bureau of Mines to determine the effect of steel reheating practices in burning natural gas on the amount of silicon required to prevent the formation of copper on steels containing up to 1 wt-pct Cu. Formation of copper, which causes surface hot shortness, was readily prevented by as little as 0.3 wt-pct Si and by 2 vol-pct excess oxygen in the furnace atmosphere when reheating steels containing up to 0.8 wt-pct Cu. Up to 0.8 wt-pct Si content and careful control of reheating conditions were necessary for steels containing 1 wt-pct Cu. Best conditions for these steels were reheating to 2,200° F (1,205° C) in burning gases containing 2 vol-pct excess oxygen, and then to higher temperatures in gases of 6 vol-pct excess oxygen. Slag and mold wash were not detrimental on steels reheated for 8 hr by a soaking-pit-type furnace schedule, but they were problematical on steels heated for 2 hr by a pusher-type furnace schedule. The effect of silicon contents on scaling rates also was determined.

Jan 1, 1974

By George J. Tamara

The urban environment presents special challenges for the design and construction of earth retention systems. Complications arising from difficult subsurface conditions are compounded by the presence of urban infrastructure and existing and prior construction. The proximity of adjacent structures as well as intense prior use can cause special concerns including the potential for archeological artifacts or contaminated ground or ground water. Utilities and structures may be particularly vulnerable to the effects of ground movement, dewatering and vibrations. Difficulty of access, congestion and limited work areas may severely restrict means and methods of construction. Dewatering may be limited or prohibited because of concerns for disposal of clean or contaminated water, depletion of aquifers, drawing of contaminants to the site or dewatering induced settlements.

Jan 1, 2003

By D. W. Olson

Garnet has been used as a gemstone for centuries. However, garnet’s angular fractures, relatively high hardness and specific gravity, being chemically inert and non-toxic and free of crystalline silica, and its ability to be recycled make garnet ideal for many industrial applications. Garnet is the general name given to a group of

Jan 1, 2005

Minerals contribute to the U.S. gross domestic prod-uct (GDP) at several levels?mining, processing and manufacturing finished products. In 2008, the estimated growth rate for the real GDP of the United States was 1.1 percent and the nominal GDP was about $14.3 trillion (Table 1). Trends in various sectors of the domestic economy are often reflected in mineral production and consumption rates. For instance, continued declines in the U.S. housing market during 2008 were reflected in further reductions in the production and consumption of cement, clays, construction sand and gravel and crushed stone (mineral commodities that are used almost exclusively in construction), and those associated with the related manufacture of goods, such as ceramic tile, heating and air conditioning equipment, paint, plumbing and sanitaryware, roofing, wiring and wallboard ? all used by the housing industry. The widespread effects of the slowing domestic economy became more apparent in the last three to six months of 2008 when prices for many mineral commodities declined sharply after reaching record highs earlier in the year, indicating significantly lower demand for those materials or products containing them.

Jan 1, 2009

By Amanda Elioff

Success of the Gold Line Eastside Extension rail tunnels in Los Angeles has prompted Metro?s planning for two new rail lines to include underground alternatives. The Westside Extension Transit Corridor alternatives include up to 17 miles of subway to be constructed in soft ground. The routes will require construction in Los Angeles? ?Potential Methane Zone,? not considered for subway construction until recently. Slurry face TBMs will likely be specified. The Regional Connector, through the downtown area, includes one underground alternative with 1.7 miles of tunnel as well as three underground stations in soft ground and rock. Challenges will include tunnel and station construction under narrow streets. This paper will describe the alternatives, planning, geologic conditions and tunneling concepts for both planning studies.

By W. –E. Marx, M. Faber, R. Pollak, I. Astberg

INTRODUCTION Essentially three strategies are pursued in parallel for protecting the underground working force in mining against the consequences of methane ignitions which might lead to explosions: • Sufficient ventilation for avoiding the formation of explosive methane-air mixtures. • Avoiding sources of ignition caused possibly by electrical equipment or friction. • Structural explosion protection for limiting explosion propagation to the farthest-going extent for the case that methane is fired because of failing of the above preventive measures taken. The corresponding methods taken in mechanized roadheadings with point-attack roadheaders in German coalmining are subject of this paper. VENTILATION In ventilation of roadheading sites the following is to be considered in respect of methane control: • Sufficient air flows by volume being cycled to the heading face for diluting released methane to safe concentrations. • Sufficient local air velocities for effective mixing of methane and air in the whole heading site, in particular directly on the heading face and underneath the roof. Furthermore, ventilation needs to be laid out in a way that cut- ting does not result in health affecting dust exposure at any working place. Accordingly, the ventilation systems shown on Fig. 1 including primary and, if necessary, secondary auxiliary ventilation air ducts as well as dedusters, are used in roadheadings. This equipment is run according to the following principles: • If the roadheader is at standstill, the heading face is ventilated by the free air jet from the blowing duct closest to the face. In this operation phase the deduster is shut-down. • During cutting, the exhaust of the blowing air duct is automatically closed, and the deduster is taken into operation. The in- coming fresh air is now locally discharged via a lateral orifice, or distributed by Coanda-type ducts from the primary or secondary ventilation air duct. In this way, a stable dust wall not disturbed by the jet of the air duct is formed in front of the heading face. Only the ventilation air stream taken in by suction of the close-to-face deduster is passed through the inby zone of the heading face (over approx. 20 m). The clean exhaust of the deduster is dischayed to the roadway in some distance outby. Immediately at the heading face, methane accumulations possibly released by cutting are diluted by compressed-air jets from air-movers located near the roof which assure more rapid motion of the air without distuhing the dust wall. • In the zone of overlapping of primary and secondary duct and the deduster - that zone possibly is poorly ventilated during cutting - sufficient local air speed is assured by Coanda-type ducts or additional ventilation jets for avoiding methane accumulation. The regulations of the inspectorate specifies geometrical conditions to be met with these configurations of ventilation equipment. In-seam roadways are ventilated at rates > 0,5 m/s. For dedusters, present-day ventilation air flows are of 600-800 m+/ min. Ventilation monitoring and control is assured by units for measuring methane and ventilation air flows. If pre-set thresholds are exceeded or fallen short of, these measuring units shut-down - dependent on potential hazard - any not intrinsically safe electrical equipment in the roadheading, either totally or in limited zones. In addition, CO-measuring units near the roadway en- trance serve for early detection of mine fires. In spite of this ventilation layout and the equipment used and in spite of the water spray systems on the cutting head (discussed later in this paper) several cases of methane ignition and subsequent burning off (however, no explosions) have been recorded in the recent past. Therefore, the above-described ventilation is nowadays complemented in many cases by machine-mounted ventilation equipment for the immediate surroundings of the cutting head. Ventilation of the surroundings of the cutting head Investigations carried out subsequent to the above-mentioned gas ignitions have shown that the high ventilation air speed necessary for rapid dilution of methane could not permanently be arrived at in the following zones: • The direct zone of cutting, in particular during sumping. • The floor zone above the debris, predominantly below the cut- ting head. Accordingly, VOEST ALPINE-Bergtechnik, a producer of mining machinery, in cooperation with DMT developed for point- alttack roadheaders a novel machine-mounted ventilation equipment, the Jet-Block" (AERO SAFE Jet-Block) shown on Fig. 2. This system allows to ventilate the above-mentioned critical zones with high flow speeds. One AS Jet-Block is mounted on each side of the boom approx. 0.5 m behind the cutting head. The blocks discharge compressed-air jets with high energy from 10 nozzles per block into the hazardous zones (Fig. 3). Two nozzles of each jet block are tangentially oriented toward the upper circumference of the cutting head, the others are arranged fan-like with orientation to the heading face underneath the cutting head and the debris. The nozzle array of the blocks as well as the com-

Jan 1, 1997

By R. Masse, J. Chameaud, J. Lafuma, R. Perraud

Estimating the risk of lung cancers for workers in uranium mines and defining the resulting dose equivalent limits have been made possible thanks to work carried out in two scientific fields : physics and epidemiology. Theoretical calculations on the basis of physical models for the former and epidemiological surveys on the mortality of uranium miners from lung cancer for the latter. However, even though considerable work has been done in these two areas, the results obtained still remain controversial on several points. The radioactive and physical instability of the aerosols present in the atmosphere of the mines and the biological complexity of the human lung which even the most sophisticated physical models can reproduce only very schematically have often proved to be insurmountable difficulties for physicists, explaining the uncertainties which subsist concerning the dose delivered to the various parts of the respiratory tract from the air breathed by miners during their work. Epidemiological investigations on the other hand, in spite of the high quality of the surveys carried out, remain open to criticism, essentially because of the very approximative estimation of the individual occupational exposure to radon daughters. This is due to the fact that uncertainties arise from the measurement of radon gas if the state of equilibrium with the daughters is not accurately known or, if the active deposit is measured, to the fact that these measurements are insufficient in number. The controversies and discrepancies which subsist with regard to the evaluation of the level of risk, and in particular for low doses, can thus be understood. In addition, epidemiological surveys cannot dissociate the carcinogenic action of radon from the synergistic or potentiating actions of tabacco and of other pollutants present in uranium mine air. Animal experiments have been largely taken into account for evaluating the toxicity of various radionuclides. This type of experiment is necessary when human data do not exist and has provided us with much information. For instance, the relative biological effectiveness of the various types of radiation, the metabolism of radionuclides and the mechanisms of cancer induction have been approached and satisfactorily resolved in this way. Concerning radon and its daughters, however, animal experiments have been used very little even though it seems apparent that they should complement epidemiological studies. For instance, whereas doubt can be cast on the data obtained from human epidemiology because of the uncertainty concerning the individual exposure of miners, those drawn from experiments are indisputable because in this case the dose is as perfectly known as the effect. In addition, the effects of radon can experimentally be appreciated separately whereas in the surveys, they cannot be dissociated from the effects of the other pollutants in the mine. Finally, there are no other means of dealing with the mechanisms of cancer induction. In order to gain any useful knowledge from this method however, the experimental model must necessarily present certain methodological guarantees and the effects seen in the animals must enable a comparison with those which appear in man. For this reason we will present here the animal model we have been using for 15 years, and will give the results obtained and compare them with human data and made a synthesis. Finally the conclusions which can be drawn will be discussed as well as their limitations with respect to the protection of uranium miners. I - MATERIAL AND METHODS Male SPF Sprague-Dawley rats were used. At the onset of the inhalations they were around 3 months old. Their small size makes it possible to expose a large number of animals at the same time. Their life-span is long enough to be able to follow the evolution of the cancers and to estimate the latency time. Finally, they present the advantage of having a very low rate of spontaneous lung cancers (SANDERS, 1979). I.1 - Three inhalation techniques were used. 1.1.1. – [Inhalation of radon decay products.] The inhalation apparatus has been described previously (CHAMEAUD et al. 1971). The first experiments utilized a room of a half cubic meter linked to a source made up of high grade uranium ore. Later on, a large installation was built with a 10 m3 inhalation chamber making it possible to expose up to 500 rats at one time at radon concentrations ranging from 100 to 10 000 WL for variable lengths of time (1 to 10 hours per day). These concentrations are higher than those to which the miners are generally exposed, but in order for the cumulated doses in man and in animal to be similar and delivered for the same fraction of their respective life-spans, the ratio of the concentrations should be approximately that of the life-spans. The concentrations of radon and its daughters during the experiments were carefully controlled thanks to multiple samplings of radon gas associated with measurements of radon decay products. I.1.2 – [ The dust inhalation chamber] has already been described : it is a dust-loading chamber where the dust content remains constant during the experiment and can hold over 20 - 30 animals (PERRAUD et al, 1970). I.1.3 – [Tobacco inhalations] take place in a smoke box

Jan 1, 1981

By K. E. Barrett

Exxon owns a uranium mill and holds two mining leases in Live Oak County, Texas, about halfway between San Antonio and Corpus Christi. The properties make up the Felder Uranium Operations which was reopened earlier this year. Exxon held an oil, gas, and other minerals lease on the J. C. Felder tract, which was adjacent to a relatively shallow uranium discovery by Susquehanna-Western, Inc. on the Marrs-McLean lease immediately south of the Felder property. Drilling in 1967 and 1968 confirmed the presence of reduced uranium mineralization in the basal sand unit of the Oakville formation on the Felder tract, which formed the major part of the roll-front deposit. In 1969 Exxon and Susquehanna-Western, Inc. entered into a sale and purchase agreement which provided for Susquehanna to mine and process Felder ore and purchase recovered uranium. Susquehanna moved an alkaline-leach mill from Wyoming, erected it on the Ray Point property, and placed it into operation late in 1970. Susquehanna mined and processed ore from the Felder and McLean properties through March 1973. Susquehanna ceased operations in March 1973. Exxon then acquired the mill and mill property. Exxon also purchased the mineral rights to the McLean lease, re-negotiated a mining lease for that property, and carried out shut-down programs for the mining and mill areas in the fall of 1973. The project was put on a standby basis until late 1973, when Exxon initiated mine feasibility studies for the project. MINE PLANNING EVALUATION The feasibility study for reopening the Felder Project began in late 1975 and was not completed until late 1976. I will discuss several areas of the feasibility study that required additional work prior to making the decision to renew operations. Ore Reserves Preparations for estimating the ore reserves began with the re-evaluation of more than 1500 natural radioactivity logs from exploration and pre-development drilling that had been completed on the property. These gamma ray logs of non-core rotary drill holes were the principal source of data used in making the estimate. Chemical assays of cores from the deposit were also used in the reserve determination. Electric resistivity and self-potential logs were made along with the gamma ray log. In December 1975 an additional core drilling project was undertaken to confirm the in-place density and radiometric equilibrium characteristics of the ore deposits. Comparison of chemical assays of cores with the U308 values calculated from the logs showed that the unoxidized ores were in radiometric equilibrium. In contrast, cores from anomalies occurring in near surface, weathered, and oxidized zones were in radiometric disequilibrium. Several important decisions were made in developing a mine plan or schedule of production from the Felder and McLean ore bodies. Disposal of Produced Mine Water: The ore bodies of the Felder Uranium Project occur at a point below the ground water table. The ore zones to be mined must first be dewatered to allow removal of mineralized material. In the open pit operations, this is accomplished by maintaining a perimeter ditch around the periphery of the open pit, allowing the interior of the pit to drain and collect into a sump and be pumped from the mine. In addition to anticipated water production from future mining operations, approximately 200M gallons of water was contained in three open pits left from prior mining operations. In two of these existing pits, the water was to be removed and disposed to allow for planned backfilling of waste material into these pits. The third pit would also have to be drained to allow continued mining of an area left from the prior operations. Essentially no ground water information was available for this area. The only data available was water production history from Susquehanna's mining operation. Two water wells were drilled early in 1976 on the Felder lease for use in obtaining hydrological data. A long term draw-down test was performed by pumping one water well and measuring water level drawdown in both the pumped well and the observation well. From these data, values for permeability and storage coefficient were calculated. These data were then used in modeling the aquifer to allow calculation of water influx into the mining area versus time. Once a schedule of water production, including the stored volume in the existing pits was calculated, alternate solutions for disposal were evaluated. The first system evaluated was a series of deep injection wells. The wells were designed to inject at a depth of approximately 3500 feet. Again very little information concerning reservoir characteristics of the receiving sand units was known. Using assumed values for reservoir permeability and storage coefficients, an injection well system was designed to allow for disposal of produced mine water. The biggest

Jan 1, 1979

By G. A. Vissac

O. R. LYONS *—I wish to thank Mr. Vissac for his compliment. I hope that his paper is not only well received, but that it will serve to bring forth more papers on the subject of thermal drying. One of the primary purposes of the work performed by Battelle for Bituminous Coal Research in investigating the thermal drying of coal was to stimulate other investigators and to get them to contribute their knowledge in the form of papers such as this one. We at Battelle and the personnel of Bituminous Coal Research are very gratified that Mr. Vissac and other persons have responded in this matter of the thermal drying of coal. I wish to state that I think that Mr. Vissac's paper is a very clear and easily understood description of a method of calculating the design requirements for a screen type drier, and I think that it would be exceedingly valuable to operators and to those who intend to purchase any type of thermal drier and use it in the future, if the manufacturers or operators who have such information for other types of driers would provide the same type of information for the other makes of driers now on the market. 1 also wish to point out—an idea that is new to me, and I know is new to most of the operators of driers in the United States-—the idea of recovering the heat that is normally lost in the coal and in the exhaust gases. This heat is not being recovered at most (of the thermal drying operations in the United States, and the possibility of recovering it should be called to the attention of every single one of those operators. I know many of them have never given any thought to the matter, but they will be interested once they realize the ease with which it could be done and the savings that could be realized. I also wish to compliment Mr. Vissac for presenting the method of analysis that he uses to determine the difficulty of drying any particular coal. It is a very simple method, and yet it seems to me that it should be a very effective, very efficient method for determining the difficulty of drying for his particular problems. C. Y. HEINER*—I do not know that I can add anything very illuminating to what Mr. Vissac has said. I think anything that Mr. Vissac said in regard to coal drying is a contribution because, to my personal knowledge, he has studied the matter carefully for many years and made many valuable contributions. I am not too familiar with coal drying problems in the east, but I know in the west we have not made enough coal drying studies. I think coal operators too often just take the coal as it is and make more or less the best of it. There are relatively few washing plants in the west now, and so the problem has not come to the front as much as it probably will in the future. In this connection, it seems to me that this matter of drying the raw coal, as Mr. Vissac brings up, is an extremely important one. We have not a continuous miner ourselves, yet, but we expect to get some this year, and we think the percentage of fine coal-—that is, minus 3/16 in.—will double. We have about 20 pct minus 3/16 in. in the 8 in. by 0 size now, and we think we will likely have 40 pct, which will have a surface moisture of the order of 8 pct. To wash it satisfactorily, we will have to dry the raw coal first in order to screen it, and after that, I suppose, there will have to be dry cleaning of some sort. We have not really used dry cleaning on fines in the west yet to my knowledge, but it is a matter that has to be faced by the industry, and I am very hopeful that Mr. Vissac's study will assist us in that connection. W. L. McMORRIS*-In my company we are preparing largely metallurgical coal for a great number of byproduct coke plants. The most outstanding thing to me about the requirements of moisture in the finished product is that there is a different requirement for almost every coke plant. Each operator has a different set of factors on which he establishes his coking costs where they involve moisture. For our corporation operations in Birmingham, my company does not produce the coal, but in Birmingham they are getting away with moistures very much higher than our plant at Clairton, Pa., would tolerate. The moisture that we have to produce for the plants along the lakefront where they are subject to much more severe weather is something else again. We have not tackled heat drying, primarily because our customers do not know what heat drying will do to the coking characteristics of the coal. If the temperature of drying can be held down

Jan 1, 1950

By Scott D. Thayer, George H. Milly

INTRODUCTION Ambient concentrations of radon and its daughter products have been measured and analyzed by a number of investigators for a variety of purposes. Principal among these purposes have been: (1) descriptive, to characterize the distribution and changes in concentrations under various conditions; (2) research in the use of radon as a tracer gas in the study of atmospheric characteristics and motions, such as eddy mass transfer, diffusivity profiles, large scale circulations, and the like; and (3) the use of radon as an atmospheric tracer in exploration for uranium deposits.* This information forms the basic data for this paper and for its placing the ambient natural, or non-anthropogenic, radon concentrations into the perspective of ambient radon health standards and lung cancer risk calculations. To enable better understanding of some aspects of the ambient radon data, review and analysis is also performed on selected measurements of radon emanation or flux from the surface of the earth into the atmosphere. These measurements have generally been made for purposes similar to those for ambient radon, i.e., (1) description of radon emanation characteristics; or (2) to support and justify the use of ambient concentration measurements in atmospheric research; or (3) in exploration for uranium. Interest is also developing in the use of such measurements for earthquake prediction. In addition, to complete the perspective, brief examination is given to anthropogenic ambient and flux radon measurements related to the mining and milling of uranium, so that comparison can he made with the values from natural sources. As a frame of reference we cite here previous summaries of studies which have presented representative values and ranges of ambient concentrations and emanation rates. H. Israel, in the Compendium of Meterorology (1951), cites eight studies of ambient radon concentrations which we have selected as representative of non-anomalous continental values. Their means generally range from [0.06 to 0.15 pCi lit-1 with the smallest reported minimum of zero and the largest maximum 0.53 pCi lit-1. The overall mean is 0.10 with a standard deviation of 0.03 pCi lit-1. Means over oceans are much smaller, and the data scarcer, with only three values ranging from 0.0004 to 0.003 pCi lit-1 and a mean of 0.0016 pCi lit-1.] Thirteen studies from Israel's list were selected as representative of mountainous terrain. These data, except for the cases of higher elevations, frequently show significantly higher values than the average cases in non-mountainous terrain described-above. The averages range from 0.10 to 0.59 pCi lit-l; the smallest minimum is zero and the largest maximum is 9.2 pCi lit-1. The overall mean is 0.30 with a standard deviation of 0.17 pCi lit-1. Israel also cites five studies of radon emanation (flux) from the earth's surface. These show a mean of 0.40 pCi-2m-2 sec-1 and a range of from 0.21 to 0.74 pCi m-2 sec-1. Data on flux are naturally scarcer in the literature than data on ambient concentrations, because of the greater interest in and utility of the ambient information. In this paper we also give special consideration to observations of the variability in time and space of radon flux rates, and to the impact of these phenomena on the use of such data for a variety of purposes. NATURAL(NON-ANTHROPOGENIC)AMBIENT RADON CONCENTRATIONS We have examined the following reports for the data selected for this category; these studies were generally intended to describe radon characteristics in the atmosphere. Jonassen and Wilkening (1970); Bradley and Pearson (1970); Wilkening (1970); Lambert, et al (1970); Pearson and Moses (1966); and DickPeddie, et al (1974). Another set of studies which was reviewed was selected because the investigators made ambient radon measurements in the course of examining the use of radon as a tracer in atmospheric research. This set consists of: Israel and Horbert (1970); Carlson and Prospero (1972); Subramanian, et al (1977); Larson (1978); Cohen, et al (1972); Hosler (1966); and Shaffer and Cohen (1972). Finally, unpublished data from uranium exploration activities (Milly and Thayer, 1976) was analyzed. [Treating the ocean cases first, the mean values are generally consistent with those quoted earlier from Israel (0.0004 to 0.003 pCi lit-1); they range from 0.001 to 0.011 pCi lit-1, with 0.003 the most frequently reported value. Continental values, from eight studies, range in means from 0.07 to 0.41 pCi lit-1 (not including mineralized areas, or "uranium country", discussed later), with maxima as high as 2.4 pCi lit -l. For comparison, the means from Israel are 0.06 to 0.15 pCi lit-1, with a maximum of 0.53 pCi lit-1. Some of these studies also present the typical decrease of-1 concentration with height to 0.01 to 0.04 pCi lit at 5 to 7 km. The vast numbers of uranium prospecting radon data of]

Jan 1, 1981

By David P. Shoemaker, Clara B. Shoemaker

It has been shown for an important class of complex transition intermetallic compounds (a, P, R, 6, and p phases) characterized by "normal" coordination [CN12 (icosahedral), CN14, CN15, CN16/ that interatomic distances nay be calculated to a good approximation as the sum of characteristic atomic radii. Two radii, one for major ligands and one for minor ligmds, are specified for each atom, except in the case of CN12 where only a miaaor-ligand radius is specified. The same appears to be true of transition-metal phases of simpler struc-ture: Laves phases (CN12, CN16), and p-tungsten phases (CN12, CN14). In the case of known examples of the more complex phases, a simple rule is given which specifies these radii. However, only a fraction of the known examples of the simpler phases obey this rule closely. To include the latter phases the rule may be modified by considering the radii as linear functions of the weighted average of the Pauling CN12 radii of the two kinds of atonzs, with the radii weighted according to the over-all chemical composition of the alloy. With very few exceptions interatomic distances for both tlze complex and the simpler transition phases can b$ predicted with this modified rule to within 0.06A. ManY intermetallic compounds are known of composition A,By, in which A is a transition element to the left of the manganese column in the periodic table and B is a transition element in or to the right of it. Frequently the coordination numbers (CN) found in these compounds are CN12 (icosahedral), CN14, CN15, and CN16 (called "normal" coordinations by Frank and Kasperl). Well-known examples are the cubic and hexagonal Laves phases which have CN12 and CN16, and the 0-tungsten (CrsO) phases which have CN12 and CN14. In the more complicated (often ternary) phases, such as the a phase,2 the Beck phases p3 and R~, the 6 phase,5 and the p p atoms occur with CN12, CN14, CN15, and (except for a) CN16; in many cases several crystallographically independent atoms of one particular CN occur in the asymmetric unit. A large number of independent interatomic distances are found in these complicated phases, varying from 20 in the a phase to 94 in the 6 phase. These distances show a large spread; they vary, for example, from 2.358 to 3.278A in the 6 phase. In our analysis of these distances we found that in each of these compounds every atomic position can be characterized by either one or two radii. The CN12 positions are characterized by a single radius, The higher coordinated positions are characterized by two radii, namely: the CN14 positions by 4 in the direction of the twelve "5-coordinated" ligands3 (called 'minor" by Frank and Kasperl) and by r:, in the direction of the two "6-coordi-nated" ligands (called "major" by Frank and Kasper); the CN15 positions by r15 for the twelve minor and r:, for the three major ligands; the CN16 positions by rlE for the twelve minor and r:, for the four major ligands. We have expressed the experimentally determined interatomic distances in observational equations as the sums of the appropriate pairs of these characteristic radii and the value of these radii have been determined by the method of least Squares. Despite their wide range, the interatomic distances could then be predicted by the sums of these atomic radii with an average deviation in any one compound of 0.06A or less. The results are summarized in Table I. Inspection of the radii thus obtained shows that in the structures in Table I the radii (in A) are given to a first approximation by the simple relationship: Where CN is the coordination number (12, 14, 15, or 16), and A = 1 for major ligands and = 0 for minor ligands. The interaLomic distances can be predicted within about 0.1A by sums of these atomic radii. Another phase belonging in this group with CN12, 14, 15, and 16 is the y phase & B7, in which A is molybdenum or tungsten and B is iron or cobalt. Recently the M%C phase has been refinedE and the observed distances also agree well with those calculated with Eq. [I]. (In the original determination of the structure of W6FeV7 the F$(II)-W(II1) distance was erroneously given as 2.84A, but we have recalculated it fro? the published parameters and found it to b? 2.57i4, in good agreement with the value of 2.6A predicted with Eq. [I.].) Many binary transition alloys are known to crystallize with the simpler structures having "nor-

Jan 1, 1964

By Bruce H. Mason

Lightweight aggregates are classified as those minerals, natural rock materials, rock-like products, and byproducts of manufacturing processes that are used as bulk fillers in lightweight structural concrete, concrete building blocks, precast structural units, road surfacing materials, plaster aggregates, and insulating fill. Other uses include architectural wall covers, suspended ceilings, soil conditioners, and other agricultural uses (Mason, 1989). One unusual agricultural use recently reported was for bedding on a crocodile farm on the south coast of Natal. It seems that female crocodiles became upset because there was no vermiculite in which to lay their eggs due to the late arrival of a consignment of vermiculite. The vermiculite was being used as a substitute for river sand to nest crocodile eggs (Griffiths, 1989). The various lightweight aggregate materials may be classified into four groups as follows: 1. Natural Lightweight Aggregate Materials-prepared by crushing and sizing natural rock materials, such as pumice, scoria, tuff, breccia, and volcanic cinders. 2. Manufactured Structural Lightweight Aggregates-prepared by pyroprocessing shale, clay, or slate in rotary kilns or on traveling grate sintering machines. 3. Byproduct Lightweight Aggregates-prepared by crushing and sizing foamed and granulated slag, cinders, and coke breeze. This group of lightweight materials, with the exception of slag, has become less significant and will not be discussed in this chapter. Other lightweight aggregates are beginning to appear in the marketplace. Some are the result of manufacturing processes on industrial byproducts and/or waste products, such as fly ash and incinerator residue (Bigner, 1992). 4. Manufactured Insulating Ultralightweight Aggregates-pre- pared by pyroprocessing ground vermiculite, perlite, and diatomite. The application of diatomite in brick and in extruded and aggregate forms has declined in recent years (Kadey, 1983) and will not be considered in this chapter. Lightweight aggregates for structural concrete and concrete masonry units, according to the American Society for Testing and Materials (1986) consist of "aggregates of low density used to produce lightweight concrete, including: pumice, scoria, volcanic cinders, tuff and diatomite; expanded shale, clay, slate, perlite, vermiculite or slag; and end products of coal or coal combustion" (Mason, 1989). Lightweight aggregates are distinguished from other mineral aggregate materials by their lighter unit weights-1 281 to 1 602 kg/m3 or less for loosely packed lightweight aggregates-as com- pared to 2 002 kg/m3 or more for crushed stone, sand, gravel, air-cooled slag, and other common mineral aggregates. The specific gravities of these lightweight aggregates are also used to classify them for use in concrete; they range from the extremely light materials, used for insulative and non-structural concrete to expanded shale, clay, slate, and slags used for structural concrete. Vermiculite and perlite are sometimes referred to as super light- weights. Insulating concrete (non-load bearing) weighing as little as 240 kg/m3 can be made with these aggregates. Natural aggregates such as pumice, pumicite, and scoria are normally made into concrete weighing about 400 to 480 kg/m3. Expanded shale, clay, and slate produced in a rotary kiln make structural concrete ranging from 1 201 to 1 842 kg/m3. Expanded shale and clay produced by sintering make concrete that ranges from 1 442 to 1 922 kg/m3. Air-cooled slag produces concrete ranging from 2 162 to 2 403 kg/m3. The low density lightweight aggregates are used primarily for insulating purposes. They have relatively low compressive strength. The middle density aggregates are used for insulation and for fill. Those at the upper end develop excellent compressive strength and are used in many structural applications (Anon., 1971). In recent years, the production of lightweight aggregates in the United States for all uses (including insulation and construction materials) has averaged about 19 Mtpy (Table 1). The production and consumption of lightweight aggregate is closely tied to the fortunes of the construction industry and the need to construct energy efficient buildings. Recent years have seen the production of lightweight aggregate approach the levels of the early 1970s. The period of 1979 to 1981 was a low point in production levels. The low levels of production were caused by significantly higher plant energy costs due to the large amounts of fuel and energy used in the production of most types of lightweight aggregate. Lower levels of construction activity also affect production levels. This chapter focuses on the use of natural lightweight aggregates and manufactured insulating ultralightweight aggregates, and on both the production and use of manufactured structural light- weight aggregates. Some additional comments are made on byproduct materials. Separate commodity chapters on vermiculite, perlite, pumice, and volcanic cinders are elsewhere in the volume. Discussion of the commodities covered elsewhere in the book will be limited to observations on their utilization and relation to other lightweight aggregate materials.

Jan 1, 1994

By S. L. Bessinger

Introduction In the design and specification of a ventilation system for an underground mine, it is necessary to make reasonably accurate estimates of the pressure losses in the various airways of the mine. These estimates can be made with little difficulty for open airways with simple geometric cross-sections, such as those cut by continuous miners or tunnel-boring machines. The situation is much different on a longwall face, where the airway's complex geometric cross section and the presence in the airway of obstructing equipment having a variety of shapes make it difficult, if not impossible, to estimate pressure loss using traditional methods of calculation. Head losses in mine entries are calculated using Atkinson's Equation. [22H= KPLQ (English) H= KP 3Q (SO (1) 5.2AA] where H = pressure loss, in. of H2O (Pa); K = friction factor, lbf•min2/ft4 (kg/m3); P = perimeter, ft (m); L = airway length, ft (m); Q = airflow quantity, ft3/min (m3/sec); and A = flow cross-sectional area, ft2 (m2) In this equation, the friction factor, K, is an empirical constant that describes the aerodynamic roughness of the airway. Typically, the K-factor for a given airway is determined by measuring the factors H, P, L, Q and A in Equation (1) and calculating K. Tables of friction factors calculated in this way are found in textbooks and handbooks that deal with mine ventilation analysis. Unfortunately, very few K-factors have been measured on longwall faces, and the accuracies of those that have been measured are entirely site specific, because of the wide variety of equipment found on longwalls. The development of a technique for prediction without mine-site measurements of the friction factor for any longwall face, regardless of its configuration, will thus be very useful in the design of ventilation systems for mines in which longwall mining is practiced. Calculation of pressure losses using Atkinson's Equation (1) and empirically determined K-factors provides accurate and useful approximations in cases where the airways have relatively simple cross sections. However, a careful analysis using the principles of fluid mechanics shows that such calculations are based on two assumptions that are not strictly correct when there are obstructions in the airway. The first assumption is that the air velocity distribution in the cross section, particularly around the perimeter, is uniform. This assumption results from the fact that the tabulated K-factor values found in the literature are based on field measurements with uniform conditions. Such uniformity does not exist in longwall airflows. The second common assumption is that the K-factor, and corresponding head loss, is independent of the Reynolds Number (NR) for a given flow. In fact, this assumption is not strictly correct, and is particularly erroneous in the case of irregular protuberances into the airflow, such as those found on a longwall face. The errors arising from the assumptions may be avoided by using K-factors calculated by a newly devised method, described below, which takes into account the fundamental principles of aerodynamic drag analysis. This new technique has two advantages: first, it is flexible enough to model any longwall, regardless of equipment configuration; second, it employs terminology and equations familiar to those who perform mine ventilation analysis, using K-factors, for which ventilation engineers have an intuitive understanding, rather than drag coefficients. To provide guidance for development of a longwall drag model, data were taken on two modern longwalls operating in substantially different conditions. Pressure measurements at Mine B were made with 200-foot (61-m) sections of 1/8-in. (3-mm) diameter plastic tubing, attached to a Dwyer Magnehelic gauge. Pressure drops were measured in 200-foot increments down the face, and summed to give the drop for the entire face length. This technique was found to produce small, repeated errors because of the number of segments required to span the longwall. At Mine A this problem was avoided by using a single, continuous, plastic tube for the entire face length. The psychrometric properties of the air were measured for both Mines A and B. A calibrated, standard vane-anemometer was used to measure the airflow on both faces. Finally, numerous dimensions were measured on both faces, and face profile drawings were obtained to allow detailed evaluation of the face equipment geometry. From this information, accurate evaluations of the average wetted perimeter and average area of the longwall face airways were made. Since the airflow is not confined to inside the powered supports at all points along the face, a quadratically weighted average of the airflows measured at various stations along the face was calculated: [n2Qavg =Qi Ii / It(2)i=1] where [Q, avg = average airflow for analytical purposes, ft3/min (m3/sec); Q= airflow at station i, ft3/min (m3/sec); 1= length of segment represented by Q, ft (m); h= length of longwall face, ft (m): and n= number of quantity measurement stations.] The quadratic weighting scheme was chosen because the

Jan 1, 1992

By G. P. Conard, R. C. Hall, J. F. Libsch

The 50 pct Fe-50 pct Co alloy undergoes a transformation from disorder to an ordered structure of the CsCl type reportedly in the vicinity of 732OC. During this process, the coercive force goes through a maximum, apparently as a result of strains associated with the coherent nucleation and growth reaction. This magnetic alloy also shows a marked increase in the ratio of residual to saturation induction, which is associated with annealing to a high degree of order with the continuous application of a magnetic field. The increase in ratio can be explained on the basis of a decrease in 90' domain boundaries and, perhaps, by an increase in anisotropy resulting from lattice distortion. THE 50 pct Fe-50 pct Co alloy undergoes a disorder-order transformation which has been reported to occur in the vicinity of 732°C1,2 The ordered structure is the CsCl type.' This magnetic alloy also shows a marked increase in the ratio of residual to saturation induction as a result of heat treatment in a magnetic field, sometimes called a response to magnetic anneal.'-' The purpose of this investigation was to study the course of the ordering reaction, the nature of the response to .heat treatment in a magnetic field, and the relation, if any, between ordering and the response. Procedure The method of approach in this investigation was to produce an initial structure as completely disordered as possible and then gradually to order the alloy by isothermal anneals at various temperatures under different conditions of the applied magnetic field. Magnetic, magnetostriction, and X-ray analyses were of primary importance in determining the property and structural changes resulting from the isothermal anneals. Rings of the 50 pct Fe-50 pct Co alloy were prepared from the elemental powders by a powder metallurgy technique, further details of which may be found in ref. 7. The initial structure was produced by annealing the specimens for ½ hr at 1000°C, cooling to and holding for ½ hr at 900°C (in the a range above the ordering temperature), and water quenching. Isothermal anneals were performed at 600°, 675°, 720°, and 740°C. For example, rings were heated to 600°C, held for a predetermined period of time, and cooled by natural cooling at a rate slightly slower than an air cool (average of 20" to 25°C per min). The tests (magnetic, etc.) were made after each heat treatment. All high temperature treatments were performed in a purified hydrogen atmosphere. The treatments at the various temperatures were carried out under one or more conditions of an applied field including 1—no field, 2—field of 20 oersteds applied on cooling only, and 3—field of 20 oersteds applied continuously during heating, holding, and cooling. Magnetic measurements were made using the standard Rowland ring technique8 with a maximum field strength of 100 oersteds. The magnetization curve, induction at 100 oersteds (B.), residual induction (Bt), and coercive force (Hc) were determined. All magnetic analysis data were based on an average of the results from three rings. A strain gage technique9 as used for the measurement of magnetostriction. The X-ray determination of the relative amount of ordered phase present was made on the ring specimen used for magnetic measurement. This was done by the back-reflection method using a rotating specimen (because of the large grain size) with unfiltered CoKa radiation and a 7 hr exposure time. Intensity measurements of the ordered line (300) were made by comparing visually the films so obtained with standard films prepared by exposing for different lengths of time a specimen given a long time anneal (high degree of order). Results In all instances the saturation induction (induction at 100 oersteds) was found to increase slightly with annealing time. This effect was small and appears to be the increase in saturation induction to be expected on ordering.10-13 The residual induction behavior was markedly influenced by the field condition during annealing, Figs. 1, 2. For the condition of no applied field, the ratio of residual to saturation induction remained essentially constant for short annealing times but showed a significant increase at longer times. With increasing annealing temperature, less time was required to produce this increase in the ratio. In the case of the 600°C anneals, the increase did not occur until approximately 20 hr, Fig. I, while on annealing at 740°C the increase was immediate, Fig. 2. Slight decreases in the ratio may be observed at 100 hr for specimens treated at 720°C and at 1 hr for those treated at 740°C. Specimens annealed in a field of 20 oersteds showed a residual to saturation induction ratio consistently higher than that for the specimens annealed without the field. The first anneal with the field (¼ hr) caused an abrupt increase in the ratio at all temperatures; thereafter, the increase in the ratio was generally similar for specimens annealed

Jan 1, 1956

By Carrol M. Beeson

Reasons are given for using a Boyle's-law porosimeter in conducting core analysis for either routine or research purposes. Among other things, it is pointed out that such a porosimeter permits the measurement of all basic properties on the same sample, thereby eliminating the sources of error inherent in the use of adjacent samples. References are made to investigations of gas adsorption on various porous materials, to show that the use of helium in Boyle's-law porosimeters reduces to negligible proportions the error due to the adsorption or desorption of the operating gas. Two Boyle's-law instruments are described. which permit accurate and rapid measurements of porosity. Schematic sketches and explanation:; are included, along with derivations of equations required in performing precise determinations. Summaries of data obtained during calibration are tabulated and analyses of the data are resented as indications of the precision and accuracy of each device. Comparisons are also shown for measurements made with each of the instruments on the same test pieces and cores. INTRODUCTION An accurate porosimeter, operating on the principle of Boyle's law. is of considerable value in the analysis of cores for either routine or research purposes. This is due primarily to the fact that the measurement of porosity with such an instrument leaves the sample free of contamination by any liquid. When used in conjunction with an extraction apparatus' for determining oil and water saturations, a Boyle's-law porosimeter permits the measurement of all basic properties on the same sample. This eliminates the sources of error inherent in the use of adjacent samples, or the necessity of determining porosity after all other properties have been obtained. Large errors may result from combining measurements made on adjacent samples in order to obtain a single property. This type of error is definitely involved when oil and water are measured with one sample, and the pore vo1ume is measured with an adjacent one. Furthermore, the source of error would be present to some extent, even if the analyst could choose the samples so they were truly adjacent from a geological standpoint. The use of adjacent samples in routine core analysis also necessarily decreases the probability of correlating core properties. For example, the chance of correlating the "irreducible" interstitial-water saturation with permeability, is bound to be greatly reduced by measuring these properties on "adjacent" samples. For research purposes, amplification is scarcely required concerning the greater flexibility of a method for measuring porosity which leaves the core free of contamination by any liquid. Even under those circumstances which require that the core be saturated with a liquid, a previous measurement of porosity with a gas is useful in determining the degree of saturation that has been attained in the process. Furthermore, for comparable accuracy, porosity usually may be determined more rapidly with a gas than with a liquid. This advantage of the Boyle's-law instrument is most outstanding when the determination time is compared with that required in obtaining porosity by evacuation of the core followed by saturation with a liquid of known density. Several porosimeters which operate on the principle of Boyle's law have been described2,3,4,5,6,7 in the literature. No comparison will be attempted between those instruments and the ones described herein. Before helium gas became readily available, Boyle's-law porosimeters were subject to an appreciable error due to the adsorption of the operating gas on the surface of the core solids. There is considerable direct and indirect evidence in the literature to support the contention that the adsorption of helium on porous solids is negligible at room temperature. In discussing the use of Boyle's-law porosimeters, Washburn and Bunting2 stated that "for most ceramic bodies dry air is a satisfactory gas, but hydrogen will be required in some instances. Helium could, of course, be employed for all types of porous materials at room temperatures or above." Howard and Hulett8 obtained evidence that the adsorption of helium was negligible at room temperatures, even on activated carbon ; for the density measured with this gas was unaffected by changes in pressure or by changes in temperature from 25 °C to 75 °C. For oil-well cores, Taliaferro, Johnson, and Dewees" obtained lower porosities with helium than with air, but apparently did not study helium adsorption. From the work of these investigators, it follows that the use of helium in Boyle's-law porosimeters reduces the error due to gas adsorption to negligible proportions. This makes it possible to construct instruments which permit the determination of porosity with (1) a high degree of accuracy, (2) with great rapidity, and (3) without contamination. THE KOBE POROSIMETER The fundamental design of the Kobe Porosimeter was developed by Kobe, Inc., which firm built about 12 of the instruments during 1936 and 1937. Since that time, seven or eight more have been constructed with their permission, making a total of about 20 that have been put into operation.

Jan 1, 1950

By D. E. Marks, Arnold, C. W, R. J. Robinson, A. E. Hoffmann

The efficiency of operation of a fixed-bed adsorption unit is infEuenced both by the absolute adsorption capacity of the bed and by the rate of adsorption. This paper describer studies of adsorption rate which were conducted in an experimental unit designed such that conditions existing in the treatment of high-pressure natural-gas mixtures could be duplicated. Variables investigated included pressure, temperature, gas composition, adsorbent particle size, depth of packed bed and gas velocity. The adequacy of a simplified mathematical model for predicting the observed phenomena was tested. A correlation is preserited which relates adsorption rate to the process variables stlldied. This correlation is useful in combination with the matheinatical model. INTRODUCTION Of the techniques available for contacting adsorbent particles with fluid streams to be treated, fixed-bed adsorption columns offer definite advantages in simplicity and ease of operation. As a result, they are often used in preference to others for such petroleum industry applications as dehydration and purification of natural gas and hydrocarbon recovery. Fixed-bed adsorption units usually consist of two or more towers filled with a desired adsorbent and operated in a cyclic manner. While one is being used to process the main flow stream, the others are undergoing regeneration to remove the adsorbed phase. When the tower on stream becomes saturated with the preferentially adsorbed material, the roles of the towers are switched, and the freshly regenerated tower is placed on stream. Cacle duration is determined by the bed capacity under the process conditions and by the flow rate through the bed. The sharpness of separation which can be effected is a function of both the absolute capacity of the bed and the rate of adsorption in the bed. The effect of rate for a particular set of conditions is evidenced by the sharpness or diffuse-ness of the adsorption front as it advances through the bed. Since data needed for design of adsorption units to treat high-pressure natural-gas systems were not available, an experimental program was designed to investigate the effects of different variables upon adsorption rate in fixed beds. In the present paper, effects of gas composition, column length, temperature, pressure, adsorbent particle size and flow rate (actual linear flow rate of the gas) are shown, and utility of a simplified mathematical model for describing the process is discussed. As gas enters the top of a cool, clean bed of adsorbent, preferentially adsorbed materials are stripped from the main flow stream by the uppermost particle layers. As these layers become saturated with a particular component, new supplies of this component are carried further down the column until fresh adsorbent is encountered. An adsorption wave thus moves through the column as material is supplied to saturate succeeding elements of the bed. Adsorption from a Multicomponent gas stream occurs as a succession of such moving waves corresponding to the different components in the gas. The leading edge of an adsorption wave for a component of a natural-gas stream moving through a bed of a common commercial adsorbent such as silica gel would be sharp but for the influence of certain broadening fac tors. These factors include a nonuniform velocity profile in the bed, longitudinal dispersion or mixing in the main gas stream, and the time required for a molecule to migrate from the main gas stream and be adsorbed at a site within the body of an adsorbent particle. If packing is uniform and the ratio of column to particle diameter is greater than approximately 15:1, the first factor is relatively unimportant' Longitudinal mixing is of importance only for the case of moderately high mass transfer with extremely slow flow rates.' The sharpness of an adsorption front, therefore, is, primarily a function of the rate of adsorption or the time required to saturate a particle of zdsorbent. Two methods for defining adsorption rate are used in this work. The first is a normalized or relative rate which describes the rate of saturation of a differential element of the packed bed. This can be measured by observing the time required for the concentration of the preferentially adsorbed material in the effluent gas from the bed to rise from zero to a value equal to that in the inlet gas stream. The second definition describes the absolute rate of mass transfer from the gaseous to the adsorbed phase. This definition is used in a mathematical description of the adsorption process. If the concentration of a component in the gas strcam leaving an adsorption column is measured and plotted as a function of time, a curve such as that shown in Fig. I results. It is seen that for a period of time the effluent gas is devoid of the component under consideration. As the bed approaches saturation, a small percentage of this material will appear in the effluent gas. The concentration will then rise with time, or increasing cumulative gas flow, until it is equal to that in the inlet gas stream. If adsorp-

By D. E. Coates, G. R. Purdy, S. V. Subramanian

The morphological stability of the planar solid-liquid interface in dilute ternary alloys, undergoing steady-state unidirectional solidification, is analyzed in terms of both the constitutional supercooling principle and the perturbation methods recently developed by Mullins and Sekerka. First, various steady-state solutions for the two solute distributions ahead of a planar interface are examined. The nature of the solutions depends on the size and concentration dependence of the off-diagonal diffusion coefficients. W~thin the framework of the constitutional supercooling principle, a cumulative contribution to instability frorn the two solutes is found to exist in the absence of diffusional interaction. It is shown that the latter can produce a further enhancement of instability or can have a stabilizing influence, depending on the form of the liquidus surface and on the sign of the solute-solute interaction. A perturbation analysis, which ignores diffusional interaction, verifies the cumulative influence of lhe solute fields and demonstrates that the Mullins-Sekerka stability criterion for binary systems (with capillarity accounted for) can be readily extended for application to ternary systems. SOME time ago, Tiller et al.' calculated the solute concentration distribution ahead of the planar solid-liquid interface of binary alloys undergoing steady-state unidirectional solidification. An earlier qualitative proposal that the transition from planar to nonplanar growth morphologies is associated solely with the onset of constitutional supercooling in the liquid layer ahead of the moving interface2 was used in conjunction with this calculation to put the now well-known constitutional supercooling (C-S) stability criterion into quantitative terms. Mullins and Sekerka,3 in a recent and very elegant analysis, established a more complete criterion (hereafter referred to as the M-S criterion). Interfacial stability was investigated by determining the time derivative of the amplitude of a sinusoidal perturbation of infinitesimal amplitude which had been introduced into the originally planar shape of the moving interface. Of particular importance is the fact that capillarity was included in the boundary conditions of their calculation. The purpose of the present paper is to extend all of this earlier work on dilute binary systems for application to dilute ternary alloy solidification. The analysis is divided into three sections. In the first the two solute distributions ahead of a moving planar interface are considered. Mathematical solutions are de- termined for situations in which: a) diffusional interaction is negligible, 6) diffusional interaction must be considered but circumstances permit use of constant diffusion coefficients, and c) the concentration dependence of off-diagonal diffusion coefficients can be described by first-order dilute solution approximations. In the next section, a stability criterion analogous to the C-S criterion is developed and the influence of diffusional interaction on interface stability is analyzed. Finally, the perturbation formalism of Mullins and Sekerka, with capillarity included in the boundary conditions, is extended for analysis of ternary systems in which diffusional interaction is negligible. The study of interface stability in binary systems usually commences with the assumption that the equilibrium distribution coefficient and the slope of the liquidus line are constant at values corresponding to infinite dilution. Similar assumptions have not been introduced into the present treatment; that is, we do not assume planar solidus and liquidus surfaces joined by tie lines which yield constant distribution coefficients. The latter involves the assumption of no ther-modynamic interaction between solute species in both the solid and liquid. We consider a ternary phase diagram for which the solidus and liquidus surfaces are, in general, nonplanar and of course pass through the corresponding binary solidus and liquidus lines. These lines are not assumed to have constant slope. In the dilute regions we are concerned with, the following assumptions are made: i) The solidus and liquidus surfaces are of a form such that both the solidus and liquidus temperatures are monotonically varying functions of each solute concentration. ii) The tie lines are such that the equilibrium distribution coefficient of a given solute is greater than unity for every point on the solidus (or liquidus) surface or it is less than unity for every point. STEADY-STATE SOLUTE DISTRIBUTIONS IN THE LIQUID As will be demonstrated in the next section, a knowledge of the steady-state solute profiles is not a necessary prerequisite for the formulation of a ternary C-S stability criterion. However, in that details, such as the complete description of the equilibrium liquidus temperature profile, require an evaluation of the solute distributions, the overall treatment is enhanced if these distributions are determined. Consider a ternary system (solvent plus solutes 1 and 2) for which a planar solid-liquid interface is in unidirectional motion at constant velocity V. At this stage it is unnecessary to limit ourselves to dilute solutions. For a stationary frame of reference the generalized forms of Fick's equations are:

Jan 1, 1969

By A. S. Nowick, C. Y. Li

It is deMonstrated that quenching from an elevated temperataupe accelerates the grain boundary relaxation in two solid solutions (aAg-Zn and a Cu-Al). This result is consistent with the proposal that, in solid solutions, grain boundary relaxation occurs by a mechanism of' self diffusion. Nevertheless, an alternative possibilitg, that quenching introduces vacancies into the boundary itself, must also be considered. THE phcnomenon of grain boundary relaxation has been well known for many years,1,2 yet the mechanism of this process is very poorly understood. One of the most interesting suggestions which relates to the mechanism of grain boundary relaxation was that of Ke,3 who claimed that the activation energy for grain boundary relaxation and for lattice self diffusion were essentially the same. The implication is therefore that the elementary step in the two processes is the same. This suggestion is particularly startling in view of the fact that activation energy for self diffusion along a grain boundary is very significantly lower than that for volume self-diffusion. Later evidence5-7 showed that there really are two grain boundary peaks, one which appears in high-purity metals, and the other (which develops at a higher temperature than the first) which appears in solid solutions beginning at solute concentrations in the range of 0.1 pct. Data for silver6 show that Kg's hypothesis is surely incorrect for the grain boundary peak in the high-purity metal, since it has an activation energy of only 22 kcal per mole, but that the hypothesis may still be correct for the grain boundary peak in various silver solid solutions, for which activation energies in the range 40 to 50 kcal per mole are observed. If the elementary step in the grain boundary relaxation process were the same as that for self-diffusion, it would be expected that the relaxation process could be hastened by quenching, 2.c. by introducing a non-equilibrium excess of lattice vacancies. Such a quenching effect has already been demonstrated in the case of another anelastic relaxation process, viz., the Zener relaxation effect. The Zener effect, which occurs in essentially all solid solutions, may be attributed to the reorientation of pairs of solute atoms in the presence of an applied shear stress,' and therefore must take place by means of a volume diffusion mechanism. The hastening of this process through quenching9 has been one way of demonstrating that atom movements in the lattice take place through a defect mechanism, presumably single vacancies. In order to see if the grain boundary relaxation is affected by quenching, it is particularly convenient to compare the grain boundary relaxation with the Zener effect, by choosing a specimen for which both relaxation effects appear. Specifically, a fine-grained sample of a solid solution shows in the curve of internal friction vs temperature, first a peak due to the Zener effect, then a second rise (and eventually a peak at substantially higher temperatures) due to the grain boundary relaxation. The same phenomena are also observable in static anelastic measurements, such as creep at very low stress levels. Thus, for the same fine-grained solid solution, the creepstrain, when plotted against log time, falls on a sigmodial curve with a sharp inflection point, due to the Zener effect, which is followed by a second rise and inflection resulting from the grain boundary relaxation. To look for a quenching effect, static measurements are preferable to the dynamic internal friction measurements, due to the fact that quenching effects tend to anneal out too rapidly at the temperatures at which the internal friction is measured.9 RESULTS AND DISCUSSION Creep experiments in torsion were carried out in an apparatus similar to that described by Ke1, whereby a wire is held under constant torque and its angular displacement is observed as a function of time. The alloy Ag-30 at. pct Znwas selected because of the large Zener relaxation that it displays. The two samples used were a "coarse grained" wire with a mean grain size about twice the diameter of the wire (diam = 0.032 in.), and a "fine-grained" wire which had several grains across the diameter. In Fig. 1 a comparison is made of the creep curves at 160°C of these two samples after they had been cooled slowly from 400°C. Curve A, which represents the coarsegrained sample, shows a unique relaxation process due to the Zener relaxation, with a relaxation time, T , in the vicinity of 100 sec. Curve B, which represents the behavior of the fine-grained sample, on the other hand, shows first the same relaxation process as that in A, followed by a turning up of the curve which corresponds to the onset of a second overlap-

Jan 1, 1962

By C. E. Armantrout, J. A. Rowland, D. F. Walsh

THE close-packed-hexagonal structure of mag-J- nesium is converted to a ductile and malleable body-centered-cubic lattice by the addition of lithium in excess of 10 pct. Further, the density of magnesium or magnesium-base alloys is decreased by additions of lithium. The practical possibilities of such alloys as a basis for uniquely light, malleable, and ductile structural materials were pointed out by Dean in 1944' and by Hume-Rothery in 1945.2 It was apparent to these investigators, however, that more complex compositions would be required if strengths sufficient for structural applications were to be developed in these alloys. In a search for strengthening additions, various investigators w have examined a number of the ternary and more complex alloys containing magnesium and lithium. An investigation of the fundamental characteristics of these alloys was undertaken by the Bureau of Mines. The investigation was initiated with a study of the magnesium-rich corner of the equilibrium diagram for the ternary system, Mg-Li-Al. The following data from published investigations of Mg-Li-A1 alloys were available: 1—a description of isothermal sections at 20" and 400°C through the Mg-Li-A1 constitution diagram by F. I. Shamrai;' 2—a diagram by P. D. Frost et al." showing approximate phase relationships at 700°F for a number of the Mg-Li-A1 alloys; and 3—diagrams showing the constitution at 500" and 700°F for the Mg-Li-A1 alloy system published by A. Jones et al.' Where compositions and temperatures permit comparison, these diagrams show disagreement. The 700°F isotherms of Frost and Jones differ only in the placement of the phase boundaries. But Sham-rai's 400°C (752°F) isotherm shows a variation in phases as well as in phase boundaries. Although rigid comparison of these different isothermal sections might not be justifiable, it seems impossible to reconcile Shamrai's construction with the isotherms of Frost or Jones. The isothermal sections presented in this paper were prepared to determine compositions which might be suitable for age hardening and to develop the general slope and placement of the various phase boundaries in the magnesium-rich corner of the diagram. Sections at 375", 200°, and 100°C were selected for investigation. In constructing these sections, the solubility of aluminum in magnesium, as reported by W. L. Fink and L. A. Willey Vn 1948, was used at the binary Mg-A1 boundary and the solubility of lithium in magnesium was obtained from the equilibrium diagram for that system as reported by G. F. Sager and B. J. Nelson" in the same year. The solubility of magnesium in lithium was determined experimentally and conforms in general to data reported by P. Saldau and F. Shamrai." Parameters for AlLi and MgI7A1, were taken from American Society for Testing Materials X-ray diffraction data cards. Experimental Procedures Although the isothermal sections presented in this paper are not unusually complex, the experimental techniques involved in their construction are made extremely difficult by the relatively high vapor pressure of lithium and the great chemical activity of both magnesium and lithium. Because of these characteristics, which make precise control of the composition of equilibrium-treated filings practically impossible, the disappearing phase method was used in preference to the parametric method in conjunction with metallographic studies. The alloys used in this investigation were melted and cast in an atmosphere of helium using a tilting-type furnace which enclosed a steel crucible and mold in a single unit. Each portion of the charge (500 to 600 g) was cleaned carefully just before placing it in the crucible; and the charge, crucible, and entire melting apparatus were evacuated and then washed with grade A helium while preheating to approximately 100°C. The alloys were melted and chill cast in an atmosphere of helium. Alloys prepared in this way were relatively free from inclusions and a fluxing treatment was considered unnecessary. The cylindrical ingots obtained were scalped and then reduced 96 pct in area by direct extrusion, yielding % in. diam rod. Sections of the rod, approximately 3 in. long, were given equilibrium heat treatments and then sampled for metallographic examination, X-ray diffraction study, and chemical analysis. The surface of each equilibrium-treated rod was machined to a depth sufficient to insure removal of contaminated material before samples for chemical analysis or X-ray diffraction study were obtained, and all decisions on microstructure were based on the examination of the central portion of the metallographic specimen. All specimens homogenized at 375°C were analyzed after this equilibrium heat treatment. When the composition of an alloy placed it in a critical area of the 200" or 100°C isothermal section, a check chemical analysis was made on a sample taken from the alloy specimen as-heat-treated at the particular temperature. Standard chemical procedures of gravimetric analysis were used in the determination of magnesium and aluminum; lithium, potassium, and sodium were determined by flame photometer methods

Jan 1, 1956

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid binary and ternary Fe-Ni-Co alloys has been measured by the Sieverts' method between 1550°and 1700°C. Solubility data and standard free energzes and enthalpies of solution for nitrogen in the alloys are presented. Interaction parameters are discussed and presented for binary and ternary alloys. MOST of the studies of nitrogen solubility in liquid metals have been directed toward the dilute alloys of iron. Several of these investigations have included measurements of the nitrogen solubility in Fe-Ni al10s'- and in Fe-Co alloys.435 There has been some work, however, that has extended across the e-i-" and F-CO" binaries. This investigation was undertaken to determine the nitrogen solubility in both binary and ternary alloys of the Fe-Ni-Co system. It was also hoped that the differences between earlier studies might be resolved. EXPERIMENTAL METHOD This investigation was made using a Sieverts' apparatus described previously." The nickel (99.85 pct) and cobalt (99.9 pct) were obtained from Sherritt-Gordon Mines, Ltd., and the iron (99.95 pct) was Fer-rovac-E obtained from Crucible Steel Co. Recrystal-lized alumina crucibles were used throughout the entire investigation with no evidence of crucible-melt reaction. Melt temperatures were measured with an optical pyrometer and the temperature scale calibrated against the melting points of the three pure metals. The emissivity of the melt was assumed to be a linear function of composition for all alloys, as has been shown for Fe-Ni alloys.lZ The emissivity of the pure metals at 1600°C were taken as 0.43 for iron, 0.44 for cobalt, and 0.45 for nickel. Using these emissivities, the trans mis sivity of the system was found to be 0.51 i 0.01. The Sieverts' method was used for this study and followed the procedures outlined previously.l' The individual metals were weighed to give about 100 g of alloy. The alloys were melted in the crucible under a partial pressure of argon. The system was evacuated, and the "hot volume" was measured with argon. To avoid the errors caused by vaporization, the melt was held under vacuum only long enough to ensure that all of the gas in the system had been removed. The influence of any small amount of vaporization on the "hot volume" was shown to be negligible by measuring the "hot volume" after a run. This measurement agreed with that made at the start of the run within the implicit error, 0.2 cc, caused by the limitations in accurately reading the buret. The solubility-pressure relationship was measured in the pure metals and in several alloy compositions throughout the ternary system. These measurements were made by admitting measured amounts of nitrogen to the system, and then determining the equilibrium nitrogen pressure above the melt. This method has the distinct advantage of higher accuracy, particularly at lower pressures, than measurements made by withdrawing gas from the system to reduce the pressure after determining the solubility at 1 atm nitrogen pressure. This latter method has a practical lower limit of about 0.4 atm where an increased error is encountered because the buret must be emptied to permit further measurements at lower pressures. By determining the relation between apparent solubility and pressure, it was possible to make a good estimate of the initial nitrogen content of the metal from the intercept of the solubility curve extrapolated to zero pressure.11 DISCUSSION The solubility data corrected to 1 atm nitrogen pressure are summarized in Table I. The reported solubility has been corrected for the initial nitrogen content of the alloys. The initial nitrogen contents fell between 0.0002 and 0.0010 wt pct, and were lower in the iron and nickel than in the cobalt. Sieverts' law was obeyed in all alloys at pressures up to 1 atm. Examples of this behavior are shown in Fig. 1. The reaction for solution of nitrogen is Taking the standard state as 1 wt pct N in the alloy and the reference state as nitrogen at infinite dilution in the alloy, and noting the adherence to Sieverts' law, K becomes the solubility of nitrogen in the alloy at 1 atm pressure. Thus the solubility data of Table I were used directly to calculate the standard free energy for the solution reaction. These results are also presented in Table I. The enthalpy of solution is also summarized in Table I as calculated from a form of the van't Hoff relation: Iron-Nickel System. The data for the solubility of nitrogen in liquid Fe-Ni binary alloys is presented in Fig. 2 along the with data of aito, Schenck et al.,' and Humbert and 1liott.l' The data for studies of nitrogen solubility in Fe-Ni alloys containing less than 20 pc t i'- are not presented in Fig. 2, although they are in good agreement with the present work. The results of this study are in good agreement with Schenck

Jan 1, 1967