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By Marcus A. Grossmann

The Institute has established this lectureship to honor the memory of a great American metallurgist, one whose fame has continued long after his passing. As one scientist recently stated it, "All metallurgical texts gradually become outdated and outmoded, except those of the great Henry Marion Howe." It seems fitting, then, that, once every year, we shouId review, in his honor, some aspects of the science in which he was such a distinguished leader, and also discuss any new data that may help to clarify our concepts. It is my privilege, for which indeed I express the deepest appreciation to this Institute, to offer for consideration a few thoughts on the toughness and fracture of hardened steels. Before proceeding to the data, I wish to express my great indebtedness to many associates whose stimulating discussions, generous contributions of data and cooperation in experiments are gratefully acknowledged. (But I wish to absolve them of any blame that may arise from the way in which their discussions and data have been used!) First, Dr. Edgar C. Bain, Vice President, Carnegie-Illinois Steel Corporation, whose amiable but merciless criticisms and always constructive and thoughtful suggestions help unfailingly to guard against pitfalls. Then to associates at Gary Steel Works, especially Mr. H. B. Wishart, Mr. W. K. Smith and Mr. V. Elliott, for great assistance in securing data. Also to Col. C. H. Greenall, Director of Laboratories, Frankford Arsenal, and his metallurgical staff, including Messrs. J. K. Desmond, H. Markus, D. F. Armiento, H. Rosenthal and Henry George, for numerous data and illustrations. Further to Dr. J. R. Low and Dr. M. Asimow, for helpful discussions of effects of states of stress during deformation and rupture, to Mr. J. M. Hodge for discussions and data, to the staff of the U. S. Steel Corporation Research Laboratory for advice and data, and to the Metallurgical Staff at Duquesne Steel Works. The individual acknowledgments will also be found under illustrations. Acknowledgment is also due to Mr. S. C. Snyder for incredibly meticulous scrutiny of manuscript. To all of these, grateful thanks. Introduction The discussion to be offered here will deal with quench-hardened steels only, and may perhaps be considered under three headings: 1. It was found that, when ferrite was precipitated in the (prior austenite) grain boundaries of hardened steel, the notch-bar toughness was much less than in pieces fully hardened. The fracture took place in the ferrite, and the loss in toughness is attributed to the lower cohesive (cleavage) strength of the ferrite, as cornpared with martensite. 2. When notch-bar impact test pieces of quenched and tempered steels were examined as to their mode of fracture, it

Jan 1, 1947

By Marcus A. Grossmann

The Institute has established this lectureship to honor the memory of a great American metallurgist, one whose fame has continued long after his passing. As one scientist recently stated it, "All metallurgical texts gradually become outdated and outmoded, except those of the great Henry Marion Howe." It seems fitting, then, that, once every year, we shouId review, in his honor, some aspects of the science in which he was such a distinguished leader, and also discuss any new data that may help to clarify our concepts. It is my privilege, for which indeed I express the deepest appreciation to this Institute, to offer for consideration a few thoughts on the toughness and fracture of hardened steels. Before proceeding to the data, I wish to express my great indebtedness to many associates whose stimulating discussions, generous contributions of data and cooperation in experiments are gratefully acknowledged. (But I wish to absolve them of any blame that may arise from the way in which their discussions and data have been used!) First, Dr. Edgar C. Bain, Vice President, Carnegie-Illinois Steel Corporation, whose amiable but merciless criticisms and always constructive and thoughtful suggestions help unfailingly to guard against pitfalls. Then to associates at Gary Steel Works, especially Mr. H. B. Wishart, Mr. W. K. Smith and Mr. V. Elliott, for great assistance in securing data. Also to Col. C. H. Greenall, Director of Laboratories, Frankford Arsenal, and his metallurgical staff, including Messrs. J. K. Desmond, H. Markus, D. F. Armiento, H. Rosenthal and Henry George, for numerous data and illustrations. Further to Dr. J. R. Low and Dr. M. Asimow, for helpful discussions of effects of states of stress during deformation and rupture, to Mr. J. M. Hodge for discussions and data, to the staff of the U. S. Steel Corporation Research Laboratory for advice and data, and to the Metallurgical Staff at Duquesne Steel Works. The individual acknowledgments will also be found under illustrations. Acknowledgment is also due to Mr. S. C. Snyder for incredibly meticulous scrutiny of manuscript. To all of these, grateful thanks. Introduction The discussion to be offered here will deal with quench-hardened steels only, and may perhaps be considered under three headings: 1. It was found that, when ferrite was precipitated in the (prior austenite) grain boundaries of hardened steel, the notch-bar toughness was much less than in pieces fully hardened. The fracture took place in the ferrite, and the loss in toughness is attributed to the lower cohesive (cleavage) strength of the ferrite, as cornpared with martensite. 2. When notch-bar impact test pieces of quenched and tempered steels were examined as to their mode of fracture, it

Jan 1, 1947

By P. Nicholls

Though the burning of fuels extends far back into antiquity, and though fuel beds are the most common and widely distributed example of chemical actions and engineering practice, there has been little attempt to group fuel beds by types or to define the principles associated with them. This paper does not profess to cover completely the subject of fuel beds. It suggests some of the over-all principles of the two more common types. No new investigational data are included, but the deductions are largely based on a recent publication of the U.S. Bureau of Mines'. Definition of Types There are three primary types of fuel beds: (I) Underfeed, in which the fuel and the air move in the same direction; (2) overfeed, in which the fuel and the air move in opposite directions; (3) crossfeed, in which the fuel and the air move at right angles to each other. The principle that fixes the type is the relation between directions of the flow of fuel and of air. Fig. 1 shows the three types diagrammatically. All other types are compounded of these three in a simple or more or less complex manner. It does not follow that these three type designations are limited to the methods used in representing them in Fig. 1; they may be turned in any direction, and as long as the relative directions of the fuel and air are the same the type is not changed. For example, A as shown .resembles a pot-type stoker, but the air and fuel can move downward as in the so-called smokeless heating boiler furnace. Also, C can be placed horizontal, as in chain-grate stokers. For this reason, the terms used to designate the three types are not all that could be desired; more logical ones could be coined, but those used probably are satisfactory until the discussion of fuel-bed types becomes more common.

Jan 1, 1936

By P. Nicholls

Though the burning of fuels extends far back into antiquity, and though fuel beds are the most common and widely distributed example of chemical actions and engineering practice, there has been little attempt to group fuel beds by types or to define the principles associated with them. This paper does not profess to cover completely the subject of fuel beds. It suggests some of the over-all principles of the two more common types. No new investigational data are included, but the deductions are largely based on a recent publication of the U.S. Bureau of Mines'. Definition of Types There are three primary types of fuel beds: (I) Underfeed, in which the fuel and the air move in the same direction; (2) overfeed, in which the fuel and the air move in opposite directions; (3) crossfeed, in which the fuel and the air move at right angles to each other. The principle that fixes the type is the relation between directions of the flow of fuel and of air. Fig. 1 shows the three types diagrammatically. All other types are compounded of these three in a simple or more or less complex manner. It does not follow that these three type designations are limited to the methods used in representing them in Fig. 1; they may be turned in any direction, and as long as the relative directions of the fuel and air are the same the type is not changed. For example, A as shown .resembles a pot-type stoker, but the air and fuel can move downward as in the so-called smokeless heating boiler furnace. Also, C can be placed horizontal, as in chain-grate stokers. For this reason, the terms used to designate the three types are not all that could be desired; more logical ones could be coined, but those used probably are satisfactory until the discussion of fuel-bed types becomes more common.

Jan 1, 1936

By P. E. Landolt

BEFORE World War I, and even prior to World War II, lithium was considered among the rare elements. Mining was limited to exploitation of a few well selected sources of rich minerals recoverable by hand cobbing methods. Within the past five years the situation has changed radically. Many new sources have been explored and developed, principally in Canada, North Carolina, and Southern Rhodesia. The prime raw material for lithium recovery is spodumene. In Southern Rhodesia, however, both petalite, a modified spodumene, and lepidolite, a lithium mica, are being mined in quantity.

Jan 4, 1957

By R. Hogg

INTRODUCTION As mineral particles are made smaller and smaller, it follows that their surfaces assume a greater and greater importance. In the extreme, the colloidal systems are characterized by the complete dominance of surface over bulk properties. Surface characteristics and properties will clearly influence any fine-particle processing operation. Comminution, for example, is a process of creating new surface. Agglomeration, on the other hand, may involve the reduction of surface area and the forces involved are generally surface forces. All mineral separations, solid-solid as well as solid-fluid, involve the treatment of two or more phases (solid plus liquid and/or gas). As the interfacial area increases, so will its effects on processing. Both physical and chemical separations are influenced by interfacial phenomena. Gravity separations are usually performed in a liquid phase and may be affected, for example, by the wetting characteristics of the solids. Flotation processes, of course, are based on the exploitation of differences in surface properties. Hydrometallurgical processing usually involves interfacial chemical reactions, e.g. leaching. The rates of such reactions depend on surface area and may be influenced by electrochemical effects in the electrical double layer at the solid-liquid interface, or by adsorption of reactant and/or product species from solution. In characterizing a mineral surface, it is important to consider first the surface area, since this determines the relative importance of the interfacial effects. The structure and chemical composition of the surface, which may depend on segregation of impurities within the solid and on adsorption from the external environment as well as on the bulk composition of the solid, will generally determine such

Jan 1, 1980

By H. W. Peirce

Identified and utilized Arizona salt deposits are of two ages: 1) Permian in the Colorado Plateau, and 2) Tertiary in the Basin and Range country. Uses include: a) storage of energy fluids in man-made solution cavities in both Permian (Supai Formation) and Tertiary (Luke salt body) salt and b) production of marketable products by solution and evaporation of tertiary salt. The two liquid petroleum storage Projects have a combined storage capacity in excess of 380 million L (100 million gal). Current production of salt products approximates 32 kt/a (32,000 stpy). Increasing demand for both storage and salt products is anticipated.

Jan 1, 1983

By E. Hornbogen, R. C. Glenn

Copper precipitates from a iron as fcc E phase without formation of intermediate compounds. In the first stage of the precipitation, spherical particles with diameters < 100A are formed at a high rate. During the second stage, the particles grow at a rate given by Zener&apos;s equation for growth of a spherical precipitate. In the third stage, growth is slower. Rod-shaped particles form after long aging times at 700°C. Maximum strengthenzng was observed at the beginning of the second step of precipitation. During plastic deformation of the aggregate, particles appear to deform initially by twinning. THE work discussed herein was part of a study of precipitation of substitutional elements from a iron. Copper was chosen as one of these substitutional elements because it has about the same atomic size as a iron, and does not form an intermetallic compound with iron. The data on the iron-copper system then available were summarized by Daniloff1 several years ago. The solubility of copper in a iron has been determined by electrical conductivity measurements,2 lattice parameter measurements,3 and by saturating thin iron foils with copper and determining the copper content.4 The results of the three investigations do not agree very well, but the value of 2.4 wt pct for the maximum solubility at 840°C seems to be the most reliable,4 Fig. 1. An alloy containing 1.23 wt pct Cu was used in our work to assure starting with a completely homogeneous material. On the copper-rich side of the diagram, there is a maximum solubility of about 4 wt pct Fe in copper at 1094°C ( phase). The precipitation of

Jan 1, 1961

By Andy B. Wallace

Veins in the Pyramid district of northwestern Nevada occur along steep fractures in Oligocene and Miocene quartz latite tuffs. The vein mineralization is zoned from a central enargite-pyrite zone outward through a complex polymetallic pyrite-tetrahedrite-sphalerite-galena-chalcopyrite-bornite-chalcocite zone, and finally to an outer zone of pyrite and galena. Wall rock alteration includes advanced argillic and sericitic envelopes along veins superimposed on district-wide propylitization. The ore distribution and alteration patterns were probably produced by an increase in pH, a decrease in sulfur fugacity, along with cooling of the migrating hydrothermal fluid.

Jan 1, 1981

By E. S. Burnett, R. V. Higgins, H. C. Miller

Information obtained from subsurface pressure and ,temperature measurements in oil wells now is recognized as invaluable to geologists, engineers, and operators of oil properties. Available only during the past few years, data resulting from subsurface-pressure surveys in oil wells already have found widespread application in the estimation of reserves and in the planning of comprehensive oil-field development programs. Subsurface pressure and temperature data, together with measurements of fluid volumes produced by individual wells and specific gravities of the fluids, also are included in the fundamental information essential in studying the movement of oil, gas and water through reservoir sands to wells. Heretofore, laboratory findings were relied upon almost entirely for information pertaining to the mechanics of flow of fluids through porous media, because there was no way to check laboratory results with actual performance in underground formations until subsurface pressure and temperature instruments were developed. Laboratory and field experiments now lend themselves to closer correlation—a fact that will accelerate the interpretation of many phenomena that occur when oil and gas flow through reservoir rocks, thousands of feet below the surface of the earth. This paper summarizes the results obtained thus far in a Bureau of Mines study of certain data pertaining to subsurface pressures and production of wells producing oil and gas (and water). For wells that have been studied, flowing naturally under volumetric or hydraulic control, a simple relation has been found between the mass rate of fluid (oil, gas and water) production and the corresponding drop in pressure in the reservoir sand. The equated relation embodies a productivity factor or "index" expressed in terms of mass rate of fluid production per pound drop in pressure through the sands. The equation as developed is an expression of the ability of a well to produce, which permits comparison on a uniform basis of the productivities of different wells. The study shows also that over the range of observed data a productivity factor

Jan 1, 1937

By L. L. Wyman

PREVIOUS studies1 by the writer dealing with the embrittlement of copper have been concerned with the behavior of various pure and deoxidized coppers when exposed to an oxidation-reduction cycle, and the consequent evaluation of these materials on the basis of their resist-ance to this action. No attention was devoted to the variations in pene-tration of embrittlement with time, when these copper materials are exposed to a strong reducing gas, such as hydrogen, nor to the variations in oxygen penetration, with time and temperature, into the "pure" coppers. The cause of the embrittlement is the reduction of the oxygen in the copper by the hot reducing gas, so that a consideration of time, tempera-ture, the occurrence of hydrogen and oxygen must be given. For the purpose of differentiating some of "the involved factors, the present work may be divided into two separate series of experiments. The first of these deals with the oxidation of purified coppers under various conditions and then the subjection of these to a standard hydrogen treatment. The second series concerns the reduction, under different conditions, of tough-pitch coppers of several oxygen contents. The resulting data will give the rates of oxidation, and of reduction, for the materials involved. The first series of experiments will reveal how rapidly copper may become oxidized, while the second series will indicate how rapidly embrittlement will penetrate into an oxygen-containing copper when it is exposed to hydrogen at different temperatures.

Jan 1, 1933

By Douglas Bunting

IN THE anthracite fields of Pennsylvania, mine fires occur with more or less regularity and their existence is an ever-present hazard in coal mining. In all probability 90 per cent. of the mine fires can be ascribed directly or indirectly to the ordinary miner&apos;s open lamp. Other causes may be smoking, electrical installations, gas explosions, gas feeders, and the communication of fire to the outcrops from ash dumps, culm banks, timber and brush fires. Fires in pump rooms, engine rooms, and barns have been largely eliminated as a result of the Act of .Assembly, approved June 15, 1911, which provides that all inside buildings, including engine rooms, pump rooms, barns etc. shall be constructed of incombustible materials. Smoking of pipes, cigars, and cigarettes should be prohibited in the mines and too much care cannot be exercised in preventing fires by enforcing all rules designed for that purpose. Mine fires that involve underground fighting are invariably dangerous, and all fires, irrespective of the method pursued in extinguishing them, involve property loss and expense. Each fire generally presents a more or less original problem, dependent on the particular conditions. Generally mine fires may be divided into two classes: Those occurring in inaccessible workings and those occurring in accessible workings. The methods pursued in extinguishing or controlling mine fires are as follows: (1) direct attack, (2) smothering by sealing, (3) flushing with silt or other solids, (4) flooding with water, (5) cutting off, (6) surrounding with incombustible materials, (7) digging out by stripping from the surface. Most fires are extinguished in their incipiency by direct attack and failure to extinguish by this method is due to late discovery, lack of water, and facilities for fighting, or improper procedure in the initial attack. Should the method first pursued be unsuccessful, careful consideration should be given in determining next the method to be adopted; then the work should be carried on as rapidly as possible and under the supervision f the most competent persons. Materials and supplies should be fur-

Jan 9, 1921

By E. W. Hart, W. R. Hibbard

The room temperature flow characteristics of a series of Cu-Cr alloys are found to be related to the amount and characteristics of the chromium-rich precipitate. The results are consistent with the theory of Fisher, Hart, and Pry, which considers the trapping to dislocation loops around precipitate particles. THE use of dispersed phases for hardening metals, particularly high temperature alloys, has been practiced for several years. Current theories describing the effects of dispersions on the basis of dislocation theory have been proposed by Mott and Nabarro.l-4 rowan," and Fisher, Hart, and Pry.8 These theories recently have been discussed by Hart,&apos; who pointed out that the experimental data available for comparison with theoretical calculations for overaged alloys are confined to studies by Gensamer, Pearsall, Pellini, and Low,8 Shaw, Sher-by, Starr, and Dorn,9 and some hitherto unpublished data on Cu-Cr alloys which will be described herein. Certain difficulties were associated with the interpretation of the first two studies. Gensamer, Pearsall, Pellini, and Low were concerned principally with interparticle spacing and did not document particle sizes. Shaw, Sherby, Starr, and Dorn included all the data in their report which was necessary for the theoretical evaluation, but their study is subject to some question1" due to difference in prior history of various specimens and due to systematic differences in particle characteristics" which appeared to be associated with differences in the magnification of their microscopic examination. The current study was undertaken to obtain critical data in a manner which avoids some of these limitations. Specimens of eight Cu-Cr alloys remaining from a previous investigation&apos;&apos; were available in the form of 100 mil sheet of the compositions shown in Table I. At 200 mil this material had been previously an- nealed ½ hr at 1000°C, water quenched, and cold rolled 50 pct. Samples were further cold rolled to a thickness of 20 mil for a total reduction of 90 pct. Sheet tensile specimens of standard geometry with a gage length 2½ in. long and 0.20 in. wide were machined from this sheet. These specimens were then annealed in a dried N2-H2 atmosphere for the times and temperatures indicated in Table I. This anneal served two purposes: 1—to obtain a fairly uniform and nearly constant grain size of 0.015 to 0.022 mm average diameter, and 2—to precipitate a fairly uniform, nearly spherical over-aged dispersion of essentially pure chromium. A typical microstructure illustrating the grain size and the uniformity of the dispersion is shown in Fig. 1. A typical dispersion illustrating the range of sizes and shapes of the particles is shown in Fig. 2. The tensile specimens were tested in the Instron equipment described in ref. 11 at room temperature at a strain rate of 0.04 in. per in. per min. Three tests were run on each alloy with sufficient repro-ducibility that a single true stress-true plastic strain curve could be drawn through the three sets of data for each alloy. Typical curves are shown in Fig. 3.

Jan 1, 1956

By C. Elbaum

If a thin layer of liquid gallium is spread on a surface of solid aluminum, the gallium penetrates high-angle grain boundaries at a very rapid rate and separation along these boundaries follows. An experiment was carried out to investigate this phenomenon. A well-annealed specimen of aluminum 99.994 pct pure, consisting of several large grains was used, Fig. 1. The dimensions of the sample were 25 mm wide by 2.5 mm thick and all the grain boundaries extended through the entire thickness of the plate. This sample was prepared by strain-annealing and, as can be seen in Fig. 1, contained one long, straight boundary. An examination of the crystal orientations showed this boundary to be a coherent twin boundary. The angular misorientations between the grains forming the other boundaries were all in excess of 20 deg. A thin layer of liquid gallium was spread on one side of the specimen at about 30°C (the melting point of gallium is 29.7"C). After the application of the liquid the temperature was lowered to about 27°C. The gallium remained liquid at this temperature and it can be seen from the A1-Ga phase diagram1 that the liquid was probably saturated with aluminum.

Jan 1, 1960

By F. W. Osterwald, C. R. Dunrud

A continuously recording seismic network was constructed in 1962 by the U.S. Geological Survey to locate epicenters and record incidence of bumps (bounces, rock bursts) that occur in the bituminous coal mines of the Book Cliffs coal field near Sunny-side, Utah. The coal is mined because of its value as coking coal, although these bumps may be a hazard to life and property. Daily records of tremors caused by bumps for 1 3/4 years indicate that a seasonal pattern, as well as a daily pattern, exists for the number of bumps that occur in a given period. Maxima occur in May and June and November and December. Marked increases at 5-day to 9-day intervals are superimposed on these seasonal maxima. The largest bumps commonly occur during seasonal maxima when the rate of occurrence suddenly decreases and the amplitude of the individual bumps increases. Knowledge of this pattern may lead to prediction of general locations and periods of increased hazard from bumps. Experience to date has shown that prediction of precise times and locations of hazardous bumps is not possible, and may never be; primarily because even a small bump can be a hazard to life and property. Some bumps or bump sequences are actually composites, consisting or two or more discrete bumps a few tenths of a second to a few seconds apart. Violent and spontaneous releases of coal and rock from faces, ribs and roofs of mines (termed bumps or bounces by miners) are a common hazard to life and property in the coal mines located in the Book Cliffs near Sunnyside, Utah (Fig. 1). These bumps

Jan 1, 1965

"In the mines producing over 500 tons per day, skips have replaced the old method of hoisting ore by cars run onto cages. In the car and cage method, two men (station tenders) trammed the loaded cars onto the one-deck cage, and as the production increased the one-deck cage was increased to two decks and later to four decks. Landing chairs at the underground stations were necessary in this method and were the cause of many serious accidents by being carelessly left in the shaft by the station-tenders when leaving one station for anotherabove. The labor and time occupied in loading the leaving cages were con¬siderable, and, at times of rapid hoisting, four men were necessary in taking off empty and caging loaded cars. This also required at the surface landing, as many as ten men on a shift to remove the loaded cars and replacing them with empties, and tram the loaded ones to the surface ore bins, where the railway cars were loaded.The skips used in Butte are generally of 100 cubic feet capacity and hold five tons of ore, and weigh 7,500 lbs. The cage above, to which the skip is attached, weighs 2,300 lbs. The skips dump automatically into a pocket of 50 tons capacity. Two men are with the skips underground and load them from 125 ton capacity ore-pockets, under each station, the bottoms of the pockets having an inclination of 50 degrees from the horizontal. At the bottom of these pockets a gate is operated by compressed air. The labor of loading the skips amounts only to the opening and closing of a valve in the air-line, the ore running by gravity into the skips.Besides the saving in labor, the use of the skips has removed the necessity of underground landing chairs in the shaft and the accidents which are inevitable where such chairs are used."

Jan 1, 1913

By C. E. Lundin, M. Hansen, D. J. McPherson

PRIOR work on the Zr-Cu phase diagram by Alli-bone and Sykes,&apos; Pogodin, Shumova, and KUGU cheva,&apos; and Raub and EngeL3 as confined largely to copper-rich alloys. The investigations of Raub and Engel were the most recent and seemingly the most complete of these. Alloys from 0 to 68.3 pct Zr were studied principally by thermal analysis and microscopic examination. These authors reported an inter metallic compound ZrCu, (1116°C melting point) and two eutectics, one at 86.3 pct Cu (977°C mp) and the other at 49 pct Cu (877°C mp). The solubility of zirconium in copper was reported to be less than 0.1 pct at 940°C. The zirconium melting stock consisted of Westing-house "Grade 3" iodide crystal bar (nominally 99.8 pct pure). It was treated by sand blasting and pickling (HF-HNO, solution) to remove the surface film of corrosion product, resulting from grade designation tests. The crystal bar was cold rolled to strip, lightly pickled again, and cut into pieces approximately 1/32 in. thick and 1/4 in. square. These were cleaned in acetone, dried, and stored for charging. The high-purity copper (spectrographic grade) was supplied by the American Smelting and Refining Co. with a nominal purity of 99.99 pct. These copper rods were rolled to strip, cut into squares the same size as the zirconium platelets, cleaned in acetone, dried, and stored. Equipment and Procedures The equipment used for melting and annealing the zirconium binary alloys and for the determination of solidus curves has been described in connection with previous work on the Ti-Si system&apos; and in recent papers in this series describing the studies on eight binary zirconium systems.5-&apos; Techniques employed for preparing and processing the alloys were also similar to those used in the above references. Ingots of 20 g were melted under a protective atmosphere of helium on water-cooled copper blocks in a nonconsumable electrode (tungsten) arc furnace. The ingots were homogenized and cold-worked prior to isothermal annealing to aid in the attainment of equilibrium. The specimens were heat-treated in Vycor bulbs sealed in vacuo or under argon, depending on the temperature of the anneal. Quenching was accomplished by breaking the Vycor bulbs under cold water. Temperature control was within ±3OC of reported temperatures. Thermal analysis was primarily relied on to determine eutectic levels, peritectic levels, and compound melting points. The induction furnace incipient melting technique was also used but did not provide the accuracy obtained by thermal analysis in this system, which involves much lower solidus temperatures than the other zirconium systems. A special technique for the determination of characteristic temperatures was employed in the case of several intermediate phases and their eutectics which displayed very small differences in melting temperatures. Specimens were sealed in Vycor bulbs and annealed at a series of very accurately controlled temperatures. Metallographic examination was then employed to reveal incipient melting. Furnaces and techniques in general were described previously.&apos; The echant used was 20 pct HF plus 20 pct HNO3 in glycerine unless otherwise stated. Results and Discussion The chemical analyses of the majority of alloys prepared for the determination of phase relationships in this system are given in Table I and a brief summary of the equilibrium anneals employed is given in Table 11. In a preliminary program, alloys containing 1, 4, and 7 pct Cu were annealed for three different times at each of the temperatures 700°, 800°, and 900°C. No change in the relative amounts of phases present was detected after 350, 150, and 75 hr at the above temperatures, respectively. The times listed in Table II were accordingly chosen as a result of these preliminary tests. Zirconium-rich alloys containing from 0.1 to 10 pct CU were reduced by cold pressing from 58 to 8 pct, depending upon thk alloy content, homogenized for 7 hr at 900°C, and then reduced 80 to 13 pct by cold rolling, again depending upon copper content. Other alloys were studied in the cast, or cast and annealed conditions. The contracted scope of investigation for this system included the range 0 to 50 atomic pct Cu. This approximate region is shown in Fig. 1. Due to evidence of phase relationships departing considerably from those proposed by Raub and Engel" in the 50 to 100 atomic pct range, the investigation was extended to cover this composition area rather thoroughly also. Fig. 2 is a drawing of the entire diagram. The labeling of some phase fields was omitted in Fig. 2 for the sake of clarity. An expanded view of the zirconium-rich region, with the experimental points necessary for its construction, is given in Fig. 3. The generally accepted value of Vogel and Tonn8 or the allotropic transformation a + 862&apos; ±5OC, was employed in the construction of these diagrams. A careful study revealed that the "Grade 3" crystal bar used in this investigation actually transforms over the approximate range 850" to 870°C, due to impurities. It must be expected that this two-phase field in unalloyed zirconium will cause some departures from binary ideality in the very dilute alloys. Zirconium-rich Alloys: The a + ß transformation temperature is decreased from 862" to about 822°C by increasing amounts of copper. Thus, a eutectoid reaction, fi ß a+ Zr,Cu, occurs at a composition of about 1.6 pct Cu. The eutectoid level was determined to lie between the alloy series annealed at 815" and 830°C. The placement of this eutectoid temperature

Jan 1, 1954

By C. F. Weinaug

In recent years, several methods have been proposed for correlation of physical properties and behavior of hydrocarbon systems. These correlations were found to be unsatis. factory for predicting differential gas liberation and shrinkage data now obtained experimentally. To achieve the desired accuracy, methods were developed to adjust the correlations with two experimental pieces of data. The required data are the saturation pressure at reservoir temperature and the specific volume or density at these conditions. The saturation pressure is used to adjust the vapor-liquid equilibrium-ratio correlations. The density measurement is used to determine the apparent density of liquid methane. With these adjustments, differential gas liberation and shrinkage are predicted within the experimental error. EQUILIBRIUM RATIOS Equilibrium ratios published by the National Gas Assn. of America&apos; were used as a basis for the calculation. The convergence pressure for the sample was determined by using a hypothetical binary system, with methane as one component and the remainder of the system lumped together to form the other component. For the critical temperature of the heavy constituent, the weight average of the critical temperatures of the ethane and heavier components was used. The correlation of pseudo-critical temperature, density and molecular weight of Matthews, Roland and Katzl was used in this calculation for the hexane and heavier fractions. Points for the critical properties of methane and the hypothetical heavy constituent were placed on a chart of the critical loci of hydrocarbon systems. A critical loci for the hypothetical binary system was drawn, and the critical pressure of this system was determined at the reservoir temperature. This critical pressure became the convergence pressure for which equilibrium ratios were read from the NGAA4 charts. The NGAA equilibrium constants for C, through C, were used for the C,; through C, fractions since they were separated on the bases of normal paraffin boiling points. The correlation of Hoffman, Crump and Hocott5 as used to estimate the equilibrium constant for the C fraction. The NGAA eauilibrium-ratio charts are based primarily on paraffin systems and have to be corrected for the presence of naphthenes and aromatics. The correlations in the literature proved too unsatisfactory for determining these corrections. EXperimental data, the saturation pressure, is used with the correlation of Soloman2 to make this adjustment. The correction factors of Soloman were cross-plotted so that the factors for ethane and heavier components were made a function of the factor for methane. a2 = 0.7927 at + 0.1646 .........(1) where a, = correction coefficient for for methane NGAA equilibrium ratio, and a2t = correction coefficient for ethane and heavier NGAA equilibrium ratios. This equation and the equation for the bubble point are solved simultaneously for the correction coefficients. The bubble-point equation is anKnXn = 1.0 . . . . (2) The equilibrium constant for the saturation pressure at reservoir temperature is used. This procedure not only corrects for the relative volatility between components, but also assures that the results will be directly related to the experimental saturation pressure. METHANE DENSITY After determining a set of equilibrium ratios, the apparent density of condensed methane at 60°F and 14.7 psia was estimated. This was found to be necessary because the correlations of Standing3 ere found to be unsatisfactory. The law of additive volumes was employed to make this calculation.

By James P. Kimball

BY the term weathering of coal is meant the process of deterioration to which under various circumstances it may be exposed at ordinary temperatures, both from outward agencies on the one hand, and on the other hand from its own constitutional qualities. This process involves along with some minor qualitative changes certain quantitative changes resulting in a gradual and limited reduction in the quantity of the organic elements, and relatively a corresponding increase of its inorganic or mineral constituents as represented by its ashes, and often in an increase of the absolute weight of the coal. In common with many mineral substances, coal absorbs oxygen

Jan 1, 1880

By James P. Kimball

By the term weathering of coal is meant the process of deterioration to which under various circi~mstances it may be exposed at ordinary temperatures, both from outward agencies on the one hand, and on the other hand from its own constitutional qualities. This process involves along with some minor qualitative changes certain quantitative changes resulting in a gradual and limited reduction in the quantity of the organic elements, and relatively a corresponding increase of its inorganic or mineral constituents as represented by its ashes, and often in an increase of the absolute weight of the coal. In common with many mineral substances, coal absorbs oxygen

Jan 1, 1880