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By D. A. Flanagan, P. B. Crawford

A study has been made of the feasibility of storing liquid meihane at low pressures in undergrohd caverns. Methane liquefies at — 258°F at atmospheric pressure. It is shown that the methane evaporation rates will rapidly decrease and cool the surrounding rock so that at the end of one month they would be between 50 Mcf/hr for a cavern of 25-ft radius and 700 Mcf/hr for a cavern of 100-ft radius. At the end of 10 years, the evaporation rates would be 18 and 100 Mcf/hr, respectively, for caverns of the same radii. The evaporation rates may be reduced by a factor of 2 to 10 by the application of insulation. The cost for mining the caverns is estimated to be $.75 to $1.25/Mcf of storage. This is substantially less than surface storage; it is believed to be safer and to result in lower maintenance, savings in space and savings in strategic materials. INTRODUCTION During the past few years, there has been an increasing interest in the economic feasibility of liquefying methane. Methane liquefaction is being considered for tanker transport; in addition, liquefaction is being reconsidered for shaving peak gas demands. Several articles have described natural gas liquefaction and the progress of the tanker in making trial runs from the United States to Great Britain to determine the feasibility of tanker transport. At the present time, pipelines are not designed to supply peak gas loads during extremely cold periods such as are oiten encountered in the North and Northeast. Gas is being stored in underground reservoirs en-route to its destination, but in many instances satisfactory storage in porous reservoirs has not been practical, especially along the Eastern seaboard where few petroleum reservoirs have been found. In England and other foreign countries, it is unlikely that satisfactory porous structures could be found, and it may be desirable to mine or excavate the rock to obtain storage. By storing the methane near the consumption point, product availability can be increased during periods of need. Methane liquefies at - 258OF at atmospheric pressure, and 1 cu ft of liquid methane will make about 600 cu ft of gaseous methane. Methane liquefaction for shaving peak gas demands was conducted in Cleveland, Ohio in the early 1940's. The Cleveland plant was designed to liquefy 4 MMcf/D of natural gas.' Development of several low-temperature processes has resulted in some improvements in the design of low-temperature storage vessels. Liquefied-methane storage vessels can be designed for various evaporation rates. The desired rate will depend on the reason for liquefaction. For shaving peak gas demands, the desired evaporation rates would be low, possibly between 0.2 and 1.5 per cent/day. For methane tanker transport and supply, the evaporation rates must be high and must equal the total daily rate of supply. It is apparent that the cost of storage facilities will depend on the objective and will vary appreciably. Surface storage of methane may cost between $3,000 and $20,000/MMscf, depending on the size and design. The failure of the surface storage vessels at Cleveland, with the resulting injury and loss of many lives, has caused considerable emphasis to be placed upon developing new, safer and improved methods of storing liquid methane. Storage of liquefied propane and butane in underground salt domes has been very satisfactory. The per-barrel cost of underground storage for any sizeable capacity is very small compared to the cost of surface storage for LPG mixtures. The larger the capacity of the underground storage, the less is the per-barrel cost. Numerous advantages appear to exist if liquefied methane could be satisfactorily stored underground, the principal advantages being increased safety, lower initial cost, lower maintenance cost, savings in space and savings in strategic materials. The purpose of this paper is to determine the feasibility of storing liquid methane underground in mined caverns. If a large spherical cavern is dug underground and is filled instantaneously with liquid methane, the surface of the sphere may approach the liquid methane temperature almost instantaneously. The temperature distribution for a sphere of radius r. in an infinite medium, initially at one temperature with spherical surface kept at T, from time t = 0, is given by Eq. 1.'

By F. S. Sinnatt

THIS paper is the outcome of an extended investigation carried out in association with Dr. L. Slater. The inquiry had been continued in various directions and a number of results are quoted from an investigation recently completed by S. H. Jenkins. In projecting the work some five years ago, the author had in view a general attack on the problem of the spontaneous combustion of coal from an angle that had received little attention. The basic idea was to obtain a "slow motion study" of the active combustion of coal. This included an examination of the conditions prevailing in a mass of coal at the moment when active combustion ceases. It was thought that, if the factors governing the extinction of combustion in coal could be definitely established, it might offer an explanation of the manner in which the spontaneous combustion of coal originates. The inquiry arose from a detailed study of the properties of fusain that the author began in 1918. Fusain seemed to possess characteristics quite distinct from the coal with which it was associated, for if it were collected into a heap and one portion were heated by a small flame the combustion would traverse the whole mass. This combustion was not accompanied by smoke and passed slowly through the heap of material. Later, it was found that coals, including anthracites, would behave in a similar manner provided they were in the form of powder and that the particles were smaller than a certain size. The limiting size of particles is a definite characteristic of the coals investigated. In view of the fact that fusain exists with coal in a state that enables it to undergo this particular form of combustion, it must be assumed, sometimes, to playa definite part in the spontaneous combustion of coal in the goaf (waste).

Jan 3, 1925

By S. C. Das. Gupta, B. S. Lement

isothermal formation of martensite occurs in the range of —65o to —197oC and is always preceded by some athermal transformation. By rapid cooling the isothermal, but not the athermal, component of transformation can be suppressed. Stabilization against isothermal transformation can be induced by cycling from below M. to room temperature. A LTHOUGH the transformation of austenite to XV martensite is generally believed to occur only on cooling, recent evidence indicates that this reaction can also occur at constant temperature. Isothermal formation of martensite was observed in tool steel by Fletcher, Averbach, and Cohen.'. They found that the hardening reaction that occurs during the quenching of a plain carbon or low carbon alloy tool steel does not stop immediately when room temperature is reached; instead austenite continues S. C. DAS GUPTA is Research Fellow, Department of Metallurgy, University of Notre Dame, Notre Dame, Ind. B. S. LEMENT, Associate Member AIME, is on the Research Staff, Department of Metallurgy, Massachusetts Institute of Technology, Cambridge, Mass. Discussion on this paper, TP 3123E, may be sent, 2 copies, to AIME by Dec. 1, 1951. Manuscript, April 16, 1951. Detroit Meeting, October 1951. This paper represents part of a thesis by S. C. Das Gupta submitted in partial fulfillment of requirements for the degree of Doctor of Philosophy in Metallurgy to the University of Notre Dame. to transform at room temperature although at a decreasing rate. Since only a small amount of austenite transforms in this fashion, isothermal formation of martensite was considered to be merely a "tailing off" effect of the main hardening reaction. Another point of view was advanced by Kurd-jumov and Maksimova"' * who reported that the austenite-martensite reaction could be suppressed by rapid cooling of a 6 pct Mn-0.6 pct C steel in liquid nitrogen and that as much as 25 pct martensite could be formed by reheating to and holding at subzero temperatures above that of liquid nitrogen. These investigators came to the conclusion that martensite is thermally nucleated at certain special regions in the austenite and subsequently grows to observable dimensions. Isothermal transformation of austenite to martensite was cited by Fisher, Hollomon, and Turnbull" as evidence supporting another nucleation and growth theory of martensite formation. According

Jan 1, 1952

By William B Price, Ralph W. Bailey

Arsenic, antimony and phosphorus are now used in the brass industry as standard inhibitors in preventing dezincification in condenser tubes. This subject has been thoroughly covered by Barry,l who de- scribed the testing procedure by total immersion of suitable specimens in a I per cent cupric chloride solution at definite temperatures. Effects of dezincification were then determined by loss in tensile strength and elongation of the test specimens after definite periods of immersion. In the crystallography of the chemical elements as tabulated by William Hume-Rothery,2 phosphorus (metallic), arsenic, antimony and bismuth are placed in group V-B and the type of crystal lattice for arsenic, antimony and bismuth is given as rhombohedral. The Metals Handbook3 lists them as 'rhobomhedral hexagonal," with the additional notation that for arsenic this is the ordinary form at 20°C.; other modifications known or probable at other temperatures. In view of these statements and of the fact that phosphorus, arsenic and antimony are effective in increasing the resistance to dezincification, it was natural to assume that bismuth would act in the same manner. A series of tests was therefore carried out employing the methods described by Barry. Much to our surprise, bismuth did not inhibit dezincification, but rather seemed to accelerate it. Tensile-test speci-

Jan 1, 1942

By Ralph W. Bailey, William B. Price

Arsenic, antimony and phosphorus are now used in the brass industry as standard inhibitors in preventing dezincification in condenser tubes. This subject has been thoroughly covered by Barry,l who de- scribed the testing procedure by total immersion of suitable specimens in a I per cent cupric chloride solution at definite temperatures. Effects of dezincification were then determined by loss in tensile strength and elongation of the test specimens after definite periods of immersion. In the crystallography of the chemical elements as tabulated by William Hume-Rothery,2 phosphorus (metallic), arsenic, antimony and bismuth are placed in group V-B and the type of crystal lattice for arsenic, antimony and bismuth is given as rhombohedral. The Metals Handbook3 lists them as 'rhobomhedral hexagonal," with the additional notation that for arsenic this is the ordinary form at 20°C.; other modifications known or probable at other temperatures. In view of these statements and of the fact that phosphorus, arsenic and antimony are effective in increasing the resistance to dezincification, it was natural to assume that bismuth would act in the same manner. A series of tests was therefore carried out employing the methods described by Barry. Much to our surprise, bismuth did not inhibit dezincification, but rather seemed to accelerate it. Tensile-test speci-

Jan 1, 1942

By Dennis A. Clark, Brent Larsson

Tunnelling today is a lot more than drilling and blasting. The developments in drilling and blasting technique have made it pos¬sible to save costs both by increasing the advance per round and optimizing the demands on the final contour. Increasing the hole depth by using longer feeds and bigger dril¬ling rigs make the drilling time shorter compared to the set up time. It is important that the deeper holes are followed up by using a suitable cut. The most common cut in Sweden today is a parallel hole cut with one or more large holes; with a diameter corresponding to the hole depth and wanted advance per round. It is often specified that smooth blasting is to be carried out with a specific drill hole spacing. It is extremely rare, however, for specifications to be issued concerning the alignment of the raw of holes closest to the contour holes. It is very easy to ruin the effect of smooth blasting altogether by firing the rest of the round carelessly with an excessively high charge distribution. The drilling and blasting of the contour holes and the line of holes closest to the contour holes is therefore an extremely important part of any underground work. Accuracy and care in connection with the drilling of contour holes is also extremely important since it is possible to reduce the amount of overbreak, the result being more rapid mucking out, smoother and more durable surfaces and also less consumption of concrete for lining purposes.

Jan 1, 1983

By J. R. Hornaday, A. E. Morris, N. A. Parlee, D. C. Carmichael

Rates of absorption and effusion of hydrogen in solid iron were measurede by a Sieverts type of apparatus. With clean a iron these rates are diffusion controlled down to 420°C and are represented by the equation D = 6.70 x e-'100' crn2 sec-I Certain surface impurities can affect these rates at all temper-atuves. Thin oxide films lower, the apparent diffusivity of annealed iron markedly. Cold-worked iron (75 pct) annealed at 430°C has practically the same solubility and diffusivity as anealed iron. THE mechanism of absorption and evolution of hydrogen in solid iron alloys is not fully understood despite the large number of investigations on the subject. While there appear to be many instances of simple solid-state diffusion control of rate, there are many cases where investigators have either concluded that surface reactions are rate controlling or that some "nondiffusible" hydrogen resides in discontinuities. The purposes of this research were 1) to develop a sound method for studying this absorption and evolution behavior, 2) to examine it in pure annealed iron, and 3) to determine the effects of important variables, such as cold work, surface condition, and composition. This paper relates the progress toward these objectives. Much of the present knowledge of the movement of hydrogen through iron alloys comes from permeability studies which involve the measurement of the rate of passage (under steady state conditions) through membranes of the order of 1 mm in thickness. This method is open to question on various grounds. If surface reactions are involved, two different surfaces operating under two different conditions must be considered. The presence of defects in the membrane even of microscopic dimensions may lead to erroneous results. A few people have studied evolution of hydrogen into vacuum, under carefully controlled (unsteady state) conditions, and some of the best diffusivity data come from these sources. Most of these methods measure rates of evolution only and thus do not make a rigorous test for reversibility of behavior. It appeared that an "unsteady state" method that would permit the measurement of both rates of evolution and absorption under controlled temperature, pressure, and other conditions would offer several advantages. Accordingly the modified Sieverts apparatus described below was designed and built. APPARATUS This apparatus is shown in Fig. 1. The sample bulb is detailed in Fig. 2. Hydrogen of 99.5 pct purity and argon of 99.99 pct purity were used. The hydrogen was deoxidized and dried by means of a Deoxo unit followed by a "Dri-erite" tower. The argon was only dried. The gas burette was graduated in tenths of a cubic centimeter, and, with the aid of a travelling magnifier, readings could be estimated to the nearest 0.01 cc. The level of mercury in the burette was adjusted by means of a leveling bulb operated by a fine screw adjustment. An electrical system, consisting of two slightly separated platinum electrodes inserted in one leg of the manometer and a small light bulb was used to obtain rapid accurate adjustment of the pressure. The capillary tubing of the Vycor sample bulb was 3 mm bore as was all tubing back to the gas burette. The samples were discs made from vacuum-melted Ferrovac-E iron of greater than

Jan 1, 1961

By W. Klement

By quenching liquid alloys, single-phase solid solutions are obtained in the ranges 0 to 42.0 at. pct Co-Au and 0 to 15 and 75 to about 100 at. pet Co-Cu. Metastable solid solutions are also found in multiphase 42.0 to 49.0 and 69. 0 to about 100 at. pet Co-Au alloys. fie inability to achieve complete solid solubiliiies in Au-co and cu-co alloys is rationalized by a conszderation of the rate processes during cooling and solidification. Trends in lattice distortion and shifts in the compositions of the melting-point minima and critical points are discussed for the binary alloys of copper, silver, and gold with some of the transition metals of the first long period. By rapidly cooling alloys from the melt, a continuous series of metastable solid solutions can often be obtained for components of similar crystal structure which normally form eutectic systems.' The eutectic system Au-Co, Fig. 1, and the peritectic system Cu-Co, Fig. 2, were investigated in order to determine the extent of the metastable solid solutions attainable with the present technique.* EXPERIMENTAL PROCEDURES Most of the alloys were prepared by melting weighed quantities of the elements (purity greater than 99.9 pct) under hydrogen in alumina crucibles by means of induction heating. After reweighing, the alloys were cast under argon into 1 mm diam wires. However, it was not possible to prepare some of the Cu-Co alloys with the requisite homogeneity (over about 1 mm3) in this way. For these alloys, reduced powders (purity greater than 99.9 pct) were mixed for 12 to 48 hr, pressed into compacts that were sintered at 1000º to 1050°C for 6 to 48 hr under hydrogen, and then furnace-cooled. Alloy charges of a few mm3, cut from the cast wires or chipped from the sintered compacts, were heated to 1550º to 1600°C in 30 sec in an alumina insert held within a graphite support and then ejected by a pulse of helium onto a lightly polished copper strip on the inner periphery of a rotating wheel. The

Jan 1, 1963

By J. S. Crump, C. R. Hocott, A. E. Hoffman

Planning of the efficient operation of a gas-condensate reservoir requires a knowledge not only of the gross phase behavior of the system but also of the equilibrium distribution of the various components between the gas and condensate phases. This equilibrium distribution can be calculated with appropriate equilibrium constants. In this paper are presented equilibrium constants determined experimentally for the oil and gas phases initially present in the same reservoir and for the gas and condensate phases of the gas cap material at a series of pressures below the original reservoir pressure. Also presented is a method for the correlation of the experimentally determined equilibrium constants. The utility of the correlation is demonstrated further by an example of its use in adjusting the equilibrium data to permit their application to another gas-condensate system of similar composition. INTRODUCTION Planning of the efficient operation of a gas-condensate reservoir requires a thorouugh knowledge not only of the gross phase behavior of the particular hydrocarbon system but also of the equilibrium distribution of the various components between the gas and condensate phases. At the initial conditions of reservoir temperature and pressure, the original hydrocarbon materials in a gas-condensate reservoir or in the gas-cap of an associated reservoir exist in a single, homogeneous vapor phase. However, some condensation of hydrocarbons to a liquid phase usually occurs in the reservoir as pressure declines incident to production. Because of this condensation. the produced gas changes composition continuously. The composition of the produced gas, as well as that of the condensed liquid, can be calculated from the composition of the original reservoir material through the application of appropriate equilibrium constants or "K"-values provided these values are known. Equilibrium constants have been used for many years in problems of surface separation of gas and oil and natural gasoline recovery. However, no satisfactory equilibrium data at reservoir conditions have been available for the higher boiling hydrocarbons which acquire abnormal volatility at high pressure and are therefore present in the gas phase in condensate reservoirs. Early work in this field indicated that the behavior of the higher boiling hydrocarbons largely determines the behavior of gas-condensate systems at high pressure.' Consequently, a portable test unit was designed to permit determination of the distribution of the heavier hydrocarbons between the gas and liquid phases of a gas-condensate system. This paper describes the test equipment and presents the results of an investigation of the reservoir fluids from an associated oil and gas reservoir in the Frio formation in Southwest Texas. Also presented is a method for correlation of the experimentally determined equilibrium constants, together with an example of the use of the method in adjusting these data for application to another gas-condensate system of similar composition. FIELD TESTING AND SAMPLING In order to determine the compositions of the reservoir fluids, field samples were secured from two different wells, one completed in the oil zone, and one completed in the gas cap. The oil well was completed through perforations in 51/2-in. casing at a depth of 6,822-6,828 ft subsea. Pressure and temperature traverses made in the well indicated the pressure and temperature to be 3,831 psig and 201 °F, respectively, at a depth of 6.828 ft subsea. Subsurface samples were taken from this well after a four-hour shut-in period.

Jan 1, 1953

By L. D. Jaffe

From data found in the literature, a method has been derived for calculating hardenability of titanium alloys from their composition. A single graph gives the contributions of each alloying element. These are simply added to a base hardenability for unalloyed titanium. Results agree satisfactorily with measured harden-abilities. RECENTLY the importance of hardenability of titanium alloys in permitting attainment of high strength and hardness has become apparent. If a titanium-base alloy has adequate hardenability for the section size and quenching practice used, it can generally be heat treated to high strength and hardness either by simple quenching or cooling from temperatures near the ß transus, by quenching and tempering (aging), or perhaps by direct isothermal transformation of ß1,2 If the hardenability is inadequate, high strength cannot be attained. Preliminary charts translating hardenability requirements for shapes quenched in various media into terms of Jominy end quenched hardenability specimens or ideal round sizes are now available for titanium alloys." The method proposed in 1942 by M. A. Grossmann for calculating hardenability of steels from composition has proved to be of great practical value.' It appeared worthwhile to see whether, using information available in the literature, a corresponding method for calculating hardenability of titanium-base alloys could be derived. Data No systematic experimental study of the hardenability of titanium-base alloys has yet been made. There is available, however, a considerable quantity of scattered data bearing on hardenability. Some investigators determined Jominy curves on one or several alloys. Others reported as-quenched hardness for specimens of a few alloys cooled at various rates or in various media. Still others gave the as-quenched hardness for systematically varied composition, using one or several cooling mediums. The measurements utilized in this work were limited to hardness. Strength measurements were not used because a low strength may reflect high hardness combined with brittleness. Since, in general, the hardness of titanium alloys goes through a peak as the cooling rate is varied from extremely fast to extremely slow, the cooling conditions at which peak hardness was found were taken as the measure of hardenability.1,2 When as-quenched hardness was found to drop as the content of an alloying element (believed to increase hardenability) was raised, this was taken as an indication that the cooling rate was faster than that giving peak hardness; otherwise, the hardness should go up because of solid solution hardening. Also, if the hardness increased on tempering at low temperatures, this was again taken to indicate that the cooling rate had been faster than that giving peak hardness. Many of the data did not indicate precisely the cooling conditions for peak hardness but merely set a maximum or a minimum bound, or a bracket. Since the sizes of specimens quenched and the location of the hardness readings were not always given, it was occasionally necessary to estimate reasonable limits for them. Only the nominal compositions were available in some cases. As quenching from below the ß transus is equivalent to starting with a mixture of a and ß phases, whose individual composition would differ from the overall composition of the alloy, only measurements after quenches from above the ß transus were used. Hardness measurements on samples heated during metal-lographic mounting were also discarded. Because of their bulk, the data used will not be reproduced. They have been or will be published elsewhere.5-22 Approach All data were first translated into terms of ideal round size. For conversion from Jominy or quenched round or sheet, the author's graphs were used." For a few furnace cools or helium quenches where cooling rates were given, conversion was made on the basis of equal cooling coefficient.23 Plots of ideal round size for peak hardness against percentage of alloying element were next made for

Jan 1, 1956

COUNCIL OF SECTION DELEGATES E H Stevens, Chairman James W Halley, Vice-Chairman George J Donaldson, Secretary The Peoples Natural Gas Co 140 Stanwix St Pittsburgh 22, Pa EXECUTIVE COMMITTEE H R Wardwell, J G Evans, H R Bianco, Harry Campbell

Jan 1, 1955

By J. H. Frye, J. W. Caum

ONE of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium,, germanium; and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, II, III, IV, and V, respectively and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-solution hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have. been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? PREVIOUS WORK Theories have been advanced to account for the hardness of solid solutions,, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Angier2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter, change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately

Jan 1, 1943

By Prakash C. Kapur

Many balling and gradation system6 generate self- similar size distributions of the agglomerates. Inspection of the experimental data shows that this is also true of the steady state distributions resulting from the granulation of coarse, partially wet powders, for example, the fertilizer feeds. This result is exploited in the derivations of a number of simple and useful relationships that are pertinent to the analysis of these agglomeration systems. The bonding liquid demand of the granulating charge is a third order polynomial function of the dimensionless ratio of feed particle size to median granule diameter in the weight-fraction distribution. The median size, in turn, is the scale factor or characteristic size parameter in the similarity distribution. The granule size distribution, therefore, is completely specified by the liquid content and the similarity function, and so are the process efficiency and the ungranulated component In the product at steady state.

Jan 1, 1977

By W. T. Allan

RAW bituminous coal has been in general use as a blast-furnace fuel in Scotland for the last century, and although its use has now been largely abandoned and it has been replaced by coke in the majority of the few furnaces which are at, present in blast in this country, coal-smelted pig iron is not yet a thing of the past; it is still being produced and mar-keted in competition with the more cheaply smelted product of the coke-fired furnace. Various factors have influenced this change in practice; the once plentiful deposits of coal of a suitable nature for the blast furnace are now not so easily obtainable; native blackband and clayband ironstones which are easily smelted in the coal-fired blast furnace, although still far from being exhausted, are not available except at a. cost that is somewhat higher than that of imported ores, making them unattractive to the ironmaster that is compelled by circumstances to smelt his iron at the lowest possible cost. Within the last 15 years overproduction of synthetic nitrogen has led to progressive reductions in the price of sulphate of ammonia, the recovery of which together with the other by-products before that time materially assisted in reducing the working costs of the coal-fired furnace. Now the sale of the by-products recovered yields a diminished profit. When the cost of the product is the only consideration the small, slow-smelting, coal-fired blast furnace cannot compare with its large, modern, coke-fired competitor. Other `considerations do not by any means all support the same side of the argument. In the smelting of pig iron to be used in the manufacture of steel where the quality of the final product depends so largely upon the control of the conversion process and so much less upon the physical quality of the pig iron used, the physical properties of the pig iron do not exert any appreciable influence upon the quality of the steel produced, therefore the methods employed in the smelting of the pig iron matter but little so long as the requisite chemical composi-tion is reached. On the other hand, in ironfounding where the simple melting of the pig iron, which is the only treatment it receives before being cast into its final form, does little or nothing to modify its original charac-

Jan 1, 1937

By J. S. Ll. Leach, L. R. Rubin, M. B. Bever

The energies of formation of ordered and disordered solid solutions of composition CusAu and the energy of ordering in this alloy were determined by tin solution calorimetry. The degree of order was measured by X-ray diffraction and electrical resistance and microhardness measurements were made on ordered and disordered specimens. AMONG the phenomena associated with the order-disorder transformation of a solid solution, the change in internal energy is of special interest because of the part it plays in the various theories of ordering. Published values for the decrease in internal energy accompanying the formation of a superlattice from a disordered solid solution of composition CuAu range from —370 to —2260 cal per gram-atom. Some of these values represent calculations based on theory and others are the results of experimental measurements. The distinction between the change in internal energy, AE, and the change in enthalpy, AH, can here be neglected, because they are approximately equal for solid-state reactions at normal pressure. An analysis of ordering by Bragg and Williams' predicts an energy change of —605 cal per gram-atom for the formation of a superlattice in the alloy Cuau from a completely random solution. Peierls" application to Cuau of Bethe'sb earest-neighbor theory yields —560 cal per gram-atom for the formation of a superlattice from a matrix which initially contains short-range order. Cowley' extended the nearest-neighbor approach to include as many as five shells of neighbors; on this basis a change in energy of —500 cal per gram-atom is expected. Eguchi," using a quantum-mechanical treatment, calculated a value of —2260 cal per gram-atom for the difference in the energy of completely disordered and completely ordered Cu,Au. Sykes and Jones- eated a completely ordered alloy and measured its heat capacity as a function of temperature. This measured heat capacity agrees closely with the corresponding value found by the Kopp-Neumann (or mixture) rule up to about 250°C and above this temperature exceeds it, especially near the critical temperature for ordering. The difference between the integrals with respect to temperature of the observed and the Kopp-Neumann heat capacities was considered to be the energy of ordering. By this method Sykes and Jones found a value of —530 cal per gram-atom. This value is not adjusted for the short-range order remaining above the critical temperature. The pres- ence of such short-range order is suggested by the difference between the measured heat capacity and the extrapolated Kopp-Neumann heat capacity immediately above the critical temperature. Values reported by Weibke and von Quadt' and by Hirabayashi, Nagasaki, and Maniwaa were obtained in the course of investigations primarily aimed at other objectives. Weibke and von Quadt measured the temperature coefficient of the electromotive force of a Cu-CuAu cell. They obtained a value of —1010 cal per gram-atom for the heat of formation of the alloy at 500°C, at which temperature there is no long-range order. They also obtained —1380 cal per gram-atom as the heat of formation of the ordered alloy at 370°C. Considering the heat of formation of the disordered alloy to be independent of temperature, they estimated the energy of ordering at 370°C as —370 cal per gram-atom. At this temperature long-range order is incomplete and the degree of order changes rapidly with temperature. Hirabayashi, Nagasaki, and Maniwa," using an annealing calorimeter, investigated an alloy containing 23.4 rather than 25.0 atomic pct Au and thus could not obtain complete order. Thelr value of the energy of ordering was —490 cal per gram-atom. Orianis has recently investigated the Au-Cu system by the galvanic emf technique. He reports values for the heats of formation of Cu-Au alloys, from which the heat of formation at 427 OC of an alloy of composition CuAu may be found by interpolation. This value is —1080 cal per gram-atom. In the work here reported, disordered and ordered alloys of composition CuAu and corresponding mixtures of gold and copper were dissolved in liquid tin and the heat effects measured. These heat effects are small, since the dissolution of gold in tin is exothermic and the dissolution of copper is endothermic. The method, therefore, yields fairly precise values of the heats of formation of disordered and ordered alloys and of the energy of ordering. Experimental Procedure The calorimeter consisted of a long-necked Dewar flask immersed in a constant temperature salt bath and has been described by Ticknor and Bever." The chief changes in this equipment were an improvement in vacuum and the replacement of the mercury thermoregulator by a resistance thermometer control circuit. The solvent, which was maintained at a constant temperature near 350°C, consisted of 500 grams of 99.99 pct pure tin. The solute samples were mixtures of gold and copper in the proportion corresponding to the composition Cu,Au or solid solutions

Jan 1, 1956

By Lawrence H. Van Vlack, Otto K. Riegger, Gerald I. Madden

The microstructural variations of periclase (MgO) in the presence of oxide liquids are examined under the steelmaking variables of: 1) temperature, 2) liquid composition, and 3) FeO additions under different oxidation levels. Attention is given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. Silicate liquids penetrate more extensively between individual periclase grains than do liquids containing high percentages of Fe2O3 Higher MgO solubilities in the liquid and lower MgO contents of the solid favor more rapid grain growth. The presence of a second solid phase reduces the periclase grain growth rate and increases the amount of the solid-to-solid contact within the oxide microstructures at high temperatures. The service suitability of a refractory depends on many factors. Two are of major importance and include 1) the thermal resistance to melting, and 2) the mechanical resistance to loads at service temperatures. Neither is a simple consequence of the service temperatures because service conditions will alter compositions, produce partial melting, and induee phase changes. Consequently, the equilibrium phase relationships have been rather thoroughly studied and give a knowledge of the thermal resistance to melting, but do not give full information about the mechanical properties because two refractories with the same types and quantities of phase may have different microstructures. Although variations of microstructures with time, temperature, and composition have been subjects for extensive investigation in metals, only a limited amount of comparable microstructural work has been performed for refractory materials.' This study was an attempt to evaluate some of the consequences of service parameters upon the microstructures of refractories so that bases may be established for the analyzing of high temperature mechanical properties. Periclase (MgO) was chosen as the refractory oxide; variables included those which are encountered under steelmaking conditions such as 1) temperature, 2) liquid composition, and 3) FeO additions under various oxidation levels. Specific attention was given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. The most closely related work on microstructures of polyphase materials is that of Van Vlack and Rieg-ger2 on the microstructure of magnesiowüstite [(Mg,Fe)O] in the presence of silica. In that work which pertained to solid solutions with less than 40 pct MgO, most of the quantitative work was performed on FeO microstructures. The chief conclusions concerning these relatively low-melting oxide solids were as follows: 1) the rate of crystalline grain growth is inversely proportional to the grain diameter, 2) grain growth proceeds more rapidly at higher temperatures but is slightly retarded by additional liquid content, and 3) a Silicate-containing liquid penetrates as a film between the individual magnesiowüstite grains independent of time, temperature, amount of liquid, or the MgO/ FeO ratio. The above observations are in contrast to prior work3 on the microstructure of silica in the presence of iron oxide-containing liquids where the liquid does not penetrate as a complete film between solid grains. The phase relationships for the compositions of the present work are shown in Fig. 1 which is a summary of the work of several investigators.4 Of importance is the fact that CaO forms a more stable structure with SiO2 and Al2O3 than do either MgO or FeO. The oxygen potential has little effect on periclase unless iron oxide is also present. The iron oxide is ferrous at moderately low oxygen levels, changing to ferric as the Oxygen potential is increased so the spinels, magnetite, and magesioferrite are formed.5 These two phases are relatively stable in air at steelmaking temperatures. I) EXPERIMENTAL PROCEDURE ractory were made with reagent grade Oxides. The magnesium oxide used was 99 pct MgO after ignition, and the iron oxide raw material had a minimum content of 99 pet Fe2O3. The CaO, SiO2, and A12O3 were also reagent grade raw materials. After mixing, the required compositions were pressed into pellets at a minimum pressure of 5000 psi to insure compaction of the raw materials and prevent excess void content. A silicon carbide element tube furnace was used with thermocouple control for sin-

Jan 1, 1963

By C. M. Weld

In the course of my professional work in China during the fall of 1907, I had an opportunity to visit the iron-ore mines at Ta-yeh in Hu-pei province (long. 114O 50t E., lat. 30' 20t N.). It occurs to me that a rescript and discussion of my notes taken at that time should be of interest, particularly as supplementing the exceedingly interesting recent paper of Thomas T. Read on The Mineral Production and Resources of China.' Ta-yeh is situated near the right bank of the Yangtze river. The mines are at an average distance of about 16 miles from the river-port Shi-hui-yao, which in turn is some 70 miles SE. of Hankom. The ores are shipped to the works of the Han-Yeh-P'ing Iron & Coal Co. at Hanyang, as also very largely to the Japanese government iron- and steel-works at Wakamatsu, Japan. Smaller qnantities have been exported to the Pacific coast of the United States. These ore-deposits have been briefly noticed in a number of publications, but, so far as I know, Mr. Read's description, in his chapter or1 the iron-ores of the Chinese Empire,2 contains the first attempt to define their geological character. In his more recent paper Mr. Read follows very closely the text of his earlier description. To quote briefly from the recent paper, he says : " The iron-ores at Ta-yeh .... lie along the contact between a marble and an intrusive body of a dark-gray syenitic rock." He refers to a figure which exhibits in plan, but not in section, the relative positions of the syenite, ore-bodies, and limestone. The contact is seen to trend approximately E-W., with the syenite on the north and the limestone on the south. " The syenite lies to the north of the marble, and a few miles farther north the marble again appears, iron-ore again being present along the contact." No litho-

Jan 1, 1913

By A. J. Bartlett

Island Creek conditions are generally referred to as ideal; yet, as at all other properties, there are all known hazards of coal mining. The hardest of these hazards to combat is the human element. The basic thought in the minds of the management of these properties is to produce coal with the utmost safety, and it has impressed upon its supervisory force that it does not want a ton of coal unless it can be produced safely. This company has instituted a mine inspection department, which reports direct to the general manager, arid all matters pertaining to safety come under the direction of this department. Through the medium of the inspection department, the management is kept in touch with the actual conditions existing in general at all mines. Inspections are made regularly arid continuously; that is, at all times while the mine!: are in operation some sections of some mines are being examined. These inspections cover all active and inactive workings. Miners are contacted in their working places and other employees at their respective, work. A thorough check is made to see that the state mining laws are complied with and that company safety rules arc being observed. Night shifts receive the same attention as day shifts. All violations and dangerous practices are brought to the attention of the plant supervisory force with suggestions and recommendations; major hazards of emergency nature are taken up immediately with the management. Periodical inspections are also made of all tipples, preparation plants, dumping and hoisting equipment, to see that all machinery is properly guarded, and walkways and platforms properly fenced; conditions of equipmcnt and mechanical defects are also reported. Reports of inspection are written in letter form and in such a manner as to give the management a picture of the existing conditions at the time of inspection. Copies of inspection reports are forwarded to the superintendents with the general manager'? comments. It has been said, "There is nothing under God's heaven that justifies. your creation or your citizenship but this gospel: ' That the next greatest

Jan 1, 1938

By A. J. Bartlett

Island Creek conditions are generally referred to as ideal; yet, as at all other properties, there are all known hazards of coal mining. The hardest of these hazards to combat is the human element. The basic thought in the minds of the management of these properties is to produce coal with the utmost safety, and it has impressed upon its supervisory force that it does not want a ton of coal unless it can be produced safely. This company has instituted a mine inspection department, which reports direct to the general manager, arid all matters pertaining to safety come under the direction of this department. Through the medium of the inspection department, the management is kept in touch with the actual conditions existing in general at all mines. Inspections are made regularly arid continuously; that is, at all times while the mine!: are in operation some sections of some mines are being examined. These inspections cover all active and inactive workings. Miners are contacted in their working places and other employees at their respective, work. A thorough check is made to see that the state mining laws are complied with and that company safety rules arc being observed. Night shifts receive the same attention as day shifts. All violations and dangerous practices are brought to the attention of the plant supervisory force with suggestions and recommendations; major hazards of emergency nature are taken up immediately with the management. Periodical inspections are also made of all tipples, preparation plants, dumping and hoisting equipment, to see that all machinery is properly guarded, and walkways and platforms properly fenced; conditions of equipmcnt and mechanical defects are also reported. Reports of inspection are written in letter form and in such a manner as to give the management a picture of the existing conditions at the time of inspection. Copies of inspection reports are forwarded to the superintendents with the general manager'? comments. It has been said, "There is nothing under God's heaven that justifies. your creation or your citizenship but this gospel: ' That the next greatest

Jan 1, 1938