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By A. Satter, J. M. Campbell

Reported herein are the results of a careful and detailed study of the non-ideal behavior of pure gases and their mixtures. Included are: (1) new data on five ternary systems composed of methane, ethane and H2 S; (2) a simple compressibility factor correlation that is inherently superior to present correlations, particularly for gases containing H2S and CO2; and(3) a detailed study of combination rules and the effect of system composition on the choice thereof. This study makes use of the rather large mass of data already available in the literature. A complete re-examination of the data and ideas presented in the last 25 years was considered desirable as a prelude to our basic concern — the effect of diluents on gas behavior. A consideration of both the macroscopic and microscopic properties of gases provides a better insight which, in turn, gives a firmer basis for improved correlation techniques. Such a study has shown that expressing the compressibility factor Z as a function of acentric factor w, as well as reduced temperature and pressure, yields a correlation that is broader in scope. The study of various combination rules has shown that better results are obtained by "tailoring" the rule used to the system composition. To do so improves the basic reality of results by overcoming some of the anomalies often found when using Kay's rule alone. Tentative recommendations are made regarding the most reliable combination rule for use with a given class of gas. The data presented are useful for estimating the direction and magnitude of the expected deviation when using a given rule. Although more work is needed, particularly around the critical region and with CO2 mixtures, the advantage of the classification scheme proposed is apparent. INTRODUCTION When one attempts to write a PVT equation to fit the data for actual gases, greater precision is obtained by the use of a multiple number of empirical constants. This has lead to multiple-constant equations such as Benedict-Webb-Rubin, Beattie-Bridgman, Keyes, etc., which are capable of yielding very precise results for pure gases in a range for which data to get the constants are available. As a matter of practicality, though, the use of such equations for gas mixtures is limited. Because of the infinite number of gas analyses available, any attempt to compile the constants needed requires a prohibitive amount of experimental data. This could be overcome by the use of a combination rule, but there is no real advantage in doing so because the end result offers no practical impovement over the Z factor correlation. The most widely used method of predicting the volumetric properties of pure gases is based upon the "theorem of corresponding states". According to this theorem, "all pure substances have corresponding molal volume at corresponding temperature and pressure if the reference point of correspondence is the critical point". Generalized compressibility charts for gases were prepared first by Cope and associates1 in 1931 and later by Brown and co-workers2 in 1932. However, the most commonly used charts are those of Dodge,3 Nelson and Obert,4 Hougen and atsson: and Standing and Katz.6 The work of Katz and co-workers has provided us with basic data for the hydrocarbons most widely used today. Their original chart6 was compared with a relatively large amount of multi-component data for gases consisting almost entirely of normal paraffin hydrocarbons. A deviation of only + 1.2 per cent was obtained.39 In the 20 years following publication of this work it has been found that the behavior of most mixtures of paraffin hydrocarbons could be predicted by this correlation within at least 5 per cent. Where difficulty has been encountered it has largely involved one or more of the following circumstances: pressures above 4,000 psig, mixtures containing large amounts of heavy ends and/or aromatics, systems in the critical region and mixtures containing polar compounds and/or CO2. The abnormal error sometimes found with such gases, not too unexpected for this method, is

By Martin A. Mayers

It has long been recognized that it would be highly desirable to be able to predict the temperatures at various points in a burning fuel bed and their variations with changes of the properties of the fuel and the rate of air supply. Experimenta1 investigations of fuel-bed temperature1-4 have not been lacking, but the absence of any theoretical background has made it impossible to use the results of these tests as a basis for prediction, except in a very general may. A mathematical analysis", based on a somewhat simplified theory of the distribution of lieat in a fuel bed, lias recently been completed by the author. Even though numerical values of some of the coefficients are not known, the calculations result in some conclusions of general significance. Thus, for example, it appears that when the temperatures throughout the fuel bed can be calculated, the rate at which ignition of the fuel by underfeed action can be maintained can also be calcu1ated. The uncertainty concerning the values of the coefficients referred to above is serious limitation on the use of that method. The following paper presents a discussion of these coefficients and includes estimates of their values based on the data now available. A brief description of the theory on which the analysis is based, and some results of the calculations showing their degree of agreement with experimental results, are presented by way of introduction to the discussion of the coefficients. For a more. extended discussion of the theory, see the A.S.M.E. paper5. Theory and Comparison with Experiment The theoretical analysis is similar to that used in the calculation of the stationary temperatures in a conducting solid in the classical theory of heat concluction. The fuel bed is pictured as a uniform, continuous, porous solid through the interstices of which air can be blown and ill which combustion can take place. The solid lias a finite thermal conductivity, so that heat may be transported in any direction, against the flow of air as well as in the same direction. While it is true that nothing

Jan 1, 1938

By Martin A. Mayers

It has long been recognized that it would be highly desirable to be able to predict the temperatures at various points in a burning fuel bed and their variations with changes of the properties of the fuel and the rate of air supply. Experimenta1 investigations of fuel-bed temperature1-4 have not been lacking, but the absence of any theoretical background has made it impossible to use the results of these tests as a basis for prediction, except in a very general may. A mathematical analysis", based on a somewhat simplified theory of the distribution of lieat in a fuel bed, lias recently been completed by the author. Even though numerical values of some of the coefficients are not known, the calculations result in some conclusions of general significance. Thus, for example, it appears that when the temperatures throughout the fuel bed can be calculated, the rate at which ignition of the fuel by underfeed action can be maintained can also be calcu1ated. The uncertainty concerning the values of the coefficients referred to above is serious limitation on the use of that method. The following paper presents a discussion of these coefficients and includes estimates of their values based on the data now available. A brief description of the theory on which the analysis is based, and some results of the calculations showing their degree of agreement with experimental results, are presented by way of introduction to the discussion of the coefficients. For a more. extended discussion of the theory, see the A.S.M.E. paper5. Theory and Comparison with Experiment The theoretical analysis is similar to that used in the calculation of the stationary temperatures in a conducting solid in the classical theory of heat concluction. The fuel bed is pictured as a uniform, continuous, porous solid through the interstices of which air can be blown and ill which combustion can take place. The solid lias a finite thermal conductivity, so that heat may be transported in any direction, against the flow of air as well as in the same direction. While it is true that nothing

Jan 1, 1938

By Earl Oliver

Superficial observation of the petroleum stabilization movement in 1932 is disappointing. Threatened overproduction persisted; waste continued; proration was violated; gasoline taxes were evaded; and, as a consequence, chaos threatened the industry as the year drew to a close. However, comparison of the movement in 1932 with its beginning a few years ago, and analyses of those influences that promote its growth as well as those which retard it, disclose some reasons for encouragement. Stabilization, as we see it, is not merely a mechanical engineering problem. It involves social engineering. By which we do not mean it is possible, or even desirable, to change the nature of men, but rather that it is possible to set up procedure that will avoid causing them to clash. It comprehends consideration of physical objects that is clearly within the field of the engineer, but it considers them only in relation to their distribution, utilization and control in harmony with philosophies that motivate men and shape current conceptions of right and wrong, or of justice and injustice if those terms be deemed more acceptable. Stabilization cannot be effected without utilizing the knowledge of the engineer, but neither can it be effected without utilizing more than comes within his traditional field of activity. In discussing the problem herein we shall endeavor to treat it briefly from that consolidated viewpoint. Rapid fluctuations in supply have characterized the oil industry from its beginning; yet only within the past ten years has an understanding begun to develop regarding the extent of waste—the degree of dissipation of natural resources—that attends the operation of the industry under the practices and laws which control it in the United States. The extent and regrettable consequences of those wastes, their underlying causes and the ease with which they could be prevented are not yet generally understood even within the industry. Producing TomoRRow' s Oil Today The interests detrimentally affected by these economic evils are vastly greater than the mere welfare of the oil industry. The problem involves the nation's supply of gasoline and other petroleum products at

Jan 1, 1933

By H. H. Podgurski, J. C. M. Li, Y. T. Chou, F. N. Davis, R. A. Oriani

When an Fe-2 pct A1 alloy is nitrogemted at 500ºC with a gus tnixture (NH3-H2) in which the nitrogen activity has been kept Lou] enough to avoid the formation of iron nitride, a two-phase alloy is generuled which consists of AlN particles and a ferrite phase cotaining a heavy network of dislocations. The amount of nitrogen contained in such an alloy, when equilibrated with the nitrogenating atmosphere, far exceeds both that needed to satisfy the normal solution requirements of a Fe and that needed to convert all of the aluninuwi to AlN. This excess nitrogen is accounted for as being trapped on dislocations, adsorbed at the ferrite -AlN interface, and as an en-Iuznced lattice solubility in strained ferrite. This excessive uptake of nitrogen had previously been attribuled by other investigators to the formation of a nonstoichiornetric aluminum nitride. Isotope exchange experiments revealed various amomts of exchargeable N14 present in the originally nitrided samples that could not be removed by reduction with HS at 500ºC. This exchangeable nitrogen has been identified us that bound to the AlN -ferrite interface. Estimates of inter facial areas in alloys containing -3 pct by weight of A1N are as high as 10 sq m per g of alloy. ThE first1 of this series of papers described the experiments forming the basis for the elucidation of the mechanism of the formation of aluminum nitride particles within an Fe-A1 alloy. It was found that not only are dislocations necessary for the nucleation of the AlN particles but also the nitriding reaction in turn produces a dense network of dislocations in the ferrite matrix. It was also observed that nitrogen in excess of that needed for the formation of stoichiometric AIN is taken up by the alloy without the formation of an iron nitride. The present paper is an analysis of the excess nitrogen sorbed by the nitrided Fe-A1 alloy which considers the structure generated by the formation of the aluminum nitride particles. Because of the high density of dislocations, this system has proved to be quite useful in studying nitrogen-dislocation interactions. Wriedt and Darken2 have already reported such studies in a cold-worked ferritic steel. EXPERIMENTAL Nitrogen Sorption. The specimens of this alloy were cold worked (50 pct reduction) to 0.011 in. thickness and chemically cleaned in a 2:1 concentrated phosphoric acid-50 pct hydrogen peroxide solution before nitrogenation. The flowing nitrogenating atmosphere (11 pct NH3-89 pct H2) was established before the ni- trogenating temperature was reached. The same gravimetric and gas-flow equipment described in an earlier paper1 was also used in this investigation. Changes in nitrogen concentration were followed gravimetrically when establishing the isotherms. In the isotope exchange experiments, concentration changes were followed volumetrically. In some instances chemical analyses (Kjeldahl method) were used to check for material balances in both the gravimetric and volumetric procedures. Our objective was to obtain reversible nitrogen sorption isotherms for alloys equilibrated with NH3-H2 gas mixtures over a large range of nitrogen activity* and temperature. The *Defined as equal to PN H /P3/2 ,where P corresponds to partial pressure in atmospheres. Actually the nitrogen activity, aN, in the alloy equals K PNH3 /p3/2H2, where K is the equilibrium constant for the reaction NH3 = N + 3/2H2. upper limit for nitrogen activity was below that which would produce iron nitride; for reasons which will become apparent later, most of the sorption studies were made in the temperature range between 400" and 500'C. The alloy sample studied most extensively in this investigation was given a series of successive reductions (100 pct H2) and nitrogenating treatments at 500°C to attain a stabilized structure. Presumably some dislocations were lost during these treatments. Throughout most of the sorption studies, temperature was held at ± 1°C and the gas-phase composition was held to k0.2 pet NH3. Based upon the results of numerous diffusion experiments with this alloy* the 'Results to be published in a third paper of this series. times chosen for equilibration were considered more than adequate, Nitrogen Isotope Exchange. The first exchange experiments were carried out by circulating a measured quantity of H2 and NH3* (with a predetermined isotopic *The NH3 was synthesized over a synthetic ammonia iron catalyst using H2, and N2, enriched with N15. AS the NH3 was formed it was removed continuously from the gas phase by circulating the mixture through a refrigerated (78ºK) trap. When most of the nitrogen had been converted to NH3, it was distilled from the trap into a glass storage vessel. composition, N15/N14) over a nitrided specimen at 450°C in a closed glass system. Attempts to reach the exchange limit isothermally, i.e., an isotopic ratio (N15/N14) in the gas phase identical with the extractable nitrogen in the nitrided alloy, were futile. The exchange rate between the gas phase and the alloy was too slow, involving many days. To circumvent the slow exchange with the gas phase, measured amounts of N15 and N14 were introduced into the alloy by nitrogenating with an NH3-H2, mixture at 500°C containing an N15/N14 ratio of 7.76; the charged specimens were then sealed by allowing an oxide film to form over them in air, and in this final condition the specimens were subjected to 500°C in vacuum for various times during which isotope exchange was allowed to proceed within the specimen. It was estab-

Jan 1, 1970

Discussion of the paper of C. M. YOUNG, presented at the St. Louis meeting, October, 1917, and printed in Bulletin No. 129, September, 1917, pp. 1369 to 1384. CARL SCHOLZ, Chicago, Ill.-Mr. Young was kind enough to' allude to the development of a mine in which I am now engaged. Several months ago the Burlington Railroad decided to open a mine in the field Which they own in Franklin County containing some 15,000 acres .(6070 ha.) of coal, ranging in thickness from 8 to 12 ft. (2 to 3.6 m.). This proposition in itself is attractive to any mining engineer, but with the backing of a large company I saw an opportunity to do some novel work in the construction line, and for several months I have been investigating and working on the problem of developing what I hope will be the largest and best equipped mine in the State of Illinois. The shaft will be sunk at a place where the coal lies at a depth of 600 ft. (182 m.) and conditions both of the surface and of the coal are ideal in every way; the seam is almost level, and we had only 7 ft. (2 m.) of surface clay to go through. We are going to hoist by skips in order to reduce the rope speed. I believe that is a long step in the direction of economy, because we not only double the output of the mine by hoisting the contents of two cars atone time, but we reduce the proportion of dead weight. In our case there will be 20 tons of coal and 18,000 lb. of skip, or 55 per cent. net and 45 per cent. tare. That, of course, necessitates less than half the rope speed for the same tonnage, and we all know that speed means power and power means cost. Skip hoisting permits the use of solid-end gate cars, which is an advantage. The cost of these cars will be in the neighborhood of $250 apiece; They are well built, with roller-bearing wheels of the most up-to-date type, spring draw-bars, and refinements of-that character which are necessary to move the loads most advantageously.

Jan 1, 1918

By O. E. Kiessling

THIS announcement of the topics relating to production control, which the Committee hopes to have discussed at the February meeting, supplements the preliminary announcement published in the November number of MINING AND METALLURGY. In the previous article, the writer indicated the kaleide-scopic nature of the questions involved in obtaining better coordination in industry, and that, as a matter of practical expediency, the discussion in February would be limited to the more obvious difficulties in industry which need attention and to those questions which the Committee thinks would be of greatest interest to members of the Institute. But while practical considerations necessitate limiting the program, free discussion of all phases of the subject is urged by 'the Committee. In a preliminary consideration of the production control problem, there loom up two questions which have to be faced: (1) First, there is the question of the extra industrial capacity necessary to meet demand during the ordinary fluctuations of business, commonly characterized as `the "business cycle." Anyone who tries to formulate a program pertaining to productive capacity must decide whether he wishes to discuss the control of business cycles. While this question may eventually lend itself to treatment, the Committee does not feel that it can be considered at present with much profit. (2) The second question arises from the existence of over-stimulated capacity above and beyond peak demands in boom times. Discussion of this topic, it is felt, would be most fruitful. How to prevent capacity from being over-stimulated to an extent beyond any hope of possible demand is a

Jan 1, 1929

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By Warren Blauvelt

IN VIEW of the enormous wastes of natural resources, of labor and of capital, due primarily to the economic environment, established by legislation, the general neglect of this phase of the problem of the elimination of waste is difficult to understand. In such a study, the engineering method of attacking a problem should be employed. The engineer does not try to solve his problem by disregarding natural laws, but by utilizing them. The successful engineer establishes an environ-ment in which forces, acting in harmony with natural laws upon an object or objects, will produce the desired results. The engineer who notices that the water level in a vessel, into which a gallon of water per minute is flowing, is two feet higher than the level in an adjacent vessel, connected therewith by a 6-in. pipe, does not assume that the law of gravity has ceased to work, or that water no longer seeks its level; he examines the connecting pipe for obstacles which prevent the free flow of water. Some editors, many reformers and most politicians tell us that the law of supply and demand no longer works; hence governmental control of commerce is necessary. Governmental control may temporarily-that is, until trial proves its futility- "insure domestic tranquility" and "promote the general welfare;" but it cannot "secure the blessings of liberty" which it cur-tails, nor can it "establish justice" which it violates.

Jan 9, 1922

By F. W. Bremmer

The experiments described in this paper constitute the preliminary work of an investigation outlined to determine the combined effects of steam and temperature on the endurance properties of certain steels. Essentially of a fundamental nature, it was found necessary, in order to make the investigation comprehensive, to test materials treated to give a wide range of properties. The work reported deals chiefly with nickel steel with one series of tests including nitriding steel. Such a study involves numerous variables, and requires an endurance-testing machine of rather special design. Testing Machines The testing machines used were designed by C. E. Weaver;l they are a modification of the White-Souther and McAdam types. Each was driven directly by an individual 1/2-hp. 115-volt direct-current motor, running at a speed of 2200 r.p.m. Fig. 1 shows the assembly drawing and Fig. 2, a photograph of one of the machines. Specimen B is held by the rotating specimen holder A inside the steam box F, which is closed at the top by a tight-fitting, elliptical cover G. The load is applied to the specimen through the rod D and bearing C. E is an oil pipe leading fromthe lubrication system to the bearing C. The steam, which comes from the power house, is admitted through an inlet (not shown in Fig. 1) at the side of the box, the drain being at the bottom. Steam packings were placed around the rod D and the rotating shaft at H, from which the water was drained by means of a vacuum, which usually showed a gage reading of about 10 in. The temperature was measured by a mercury thermometer, and the pressure by a steam gage. Method of Applying Load After the motor has been started and the specimen as a consequence put in rotation, the load is applied by placing the foot pedal A (Fig. 2) in contact with electromagnet B, the winding of which is connected electrically in series with the motor. This operation releases the support under the weights that constitute the load. By this means the load

Jan 1, 1930

Jan 1, 1885

By W. C. Meyer

In an effort to conserve and extend oil resources, the use of powdered coal-in-oil mixtures (COM) as an alternate fuel in oil-fired boilers is receiving increasing attention. For the approach to be successful, some degree of stability of the suspension against settling is needed. The variety of means available to achieve stability of this nonaqueous slurry is reviewed along with some of the physical and chemical concepts which underlie each method.

Jan 1, 1983

cation received from Brigadicr General Thos. G. Hanson said: "It is my painful duty to communicate to you the fact of the loss of your son, Martin F. Bowles. About 11 o'clock on the night of September 3, Lieutenant Bowles, with Lieutenant Joseph B. Keckler, 355th Infantry, in command of a reconnoitering patrol of our troops, encountered the enemy. In the ensuing engagement your son received a rifle bullet through his heart. His death was instantaneous and painless. His remains were intcrred with full military honors on the 4th of September." He was promoted to First Lieutenant, but his commission did not reach him before his death. He was president of the Missouri Mining Association, Missouri School of Mines, for the year 1916-17.

Jan 1, 1920

cation received from Brigadicr General Thos. G. Hanson said: "It is my painful duty to communicate to you the fact of the loss of your son, Martin F Bowles. About 11 o'clock on the night of September 3, Lieutenant Bowles, with Lieutenant Joseph B. Keckler, 355th Infantry, in command of a reconnoitering patrol of our troops, encountered the enemy. In the ensuing engagement your son received a rifle bullet through his heart. His death was instantaneous and painless. His remains were intcrred with full military honors on the 4th of September." He was promoted to First Lieutenant, but his commission did not reach him before his death. He was president of the Missouri Mining Association, Missouri School of Mines, for the year 1916-17.

Jan 1, 1920

By Alfred H. Hesse, Edwin T. Myskowski

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

By Edwin T. Myskowski, Alfred H. Hesse

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

By H. T. Shore, J. M. Schultz

A number of experimental rnethods—X-ray powder diffractometry, Laue photography, X-ray small-angle scattering, and transmission electron microscopy and dijfraction—have been utilized to examine the morphology associated with precipitation from the terminal, g, solid solution of a Zn-1 pct Cu alloy. A significant age hardening was observed in a 1 pct Cu alloy. X-ray and electron diffraction results showed that the structural inhomogeneities associated with the hardening were isotructural with the matrix. The average size and shape of the inhomogeneities were deduced from the electron microscopy and X-ray small-angle scattering. The preprecipitates are hexagonal platelets some 300? in diam. and some twelve unit cells thick. The orientation of the platelets was deduced from Laue photographs and electron diffraction. The platelet plane is (0001). When a large amount of pre-precipitation is present in a localized volume the new lattice is often disoriented by a rotation about (0001) of of the matrix. WhILE dilute Zn-Cu alloys have been commercially important for some 50 years, relatively very little is known metallographically about this material. The "Zilloys", zinc with about 1 wt pct Cu and sometimes a small addition of magnesium, are used to produce rolled zinc which is harder and stronger than that produced by other rollable zinc alloys.' According to the phase diagrams of the zinc-rich side of the Cu-Zn system, such dilute Zn-Cu alloys should age-harden;2-5 the solubility of copper in zinc, g-phase, at 424°C is 2.68 pct, while at 0°C it is only to 0.3 pct. However, the published literature on the aging of this system appears to be limited to a documentation of the contraction of 1, 2, and 3 pct Cu alloys aging at 95°c,6 and an attempt to measure changes in lattice parameters during aging.' In the latter work, no lattice parameter changes were detected, although a broadening of the highest-angle lines was detected and considerable diffuse scattering was observed. Micro-structural investigations have been limited to the latest stage of aging, wherein Widmanstatten precipitates are formed.3,47 These alloys are of interest for still another reason. The two most zinc-rich phases in the Cu-Zn system, 77 and E, are both hcp. Moreover, the change in a, between 17 and t for a 1 wt pct Cu alloy is onlv 3.64 -,~ct: the change in Co is 12.0 ict. It would be anticipated that precipitation in such a material might occur through metastable phases or G.P. zones with epitaxy along mutual 0001 planes. The goals of the present work are aimed at partially filling the void of knowledge concerning the early stages of precipitation from the g phase. In particular, we have attempted to document the magnitude of the age hardening of this system and to determine the size, shape, and orientation within the matrix of the elements of precipitation in an early stage of condensation. EXPERIMENTAL A) Specimen Preparation. Specimens were prepared In two somewhat different ways, one method being used for X-ray Laue and diffractometer measurements, optical microscopy, and Rockwell hardness measurements and the other used for electron microscopy and X-ray small-angle scattering. In the first case zinc and copper in the proper proportions to yield a 1 wt pct Cu alloy were melted together in a closed graphite crucible. Castings so made were free of apparent segregation or oxidation. The castings were then solution-annealed at 400°C for several days and then quenched in water to room temperature. Filings of portions of the specimens were made for use as X-ray powder diffractometry specimens. The electron microscope material was made as follows. Castings were made under vacuum with copper powder placed inside a hollow zinc cylinder to insure good contact of the materials. These 1 wt pct Cu pieces were then rolled to 0.1 mm with an intermediate anneal in vacuo. The rolled sheets so formed were then annealed for about 6 hr at 225°C. Finally the specimens were electropolished slowly until thin enough for transmission electron microscopy. The polishing is discussed in greater detail in the Results section. B) Measurements. X-ray measurements of three types were performed. A G.E. XRD-5 diffractometer was used to examine powders of the alloy for identification of second-phase material. A Kratky small-angle camera, also operating from a G.E. tube, was used to investigate the sizes of small precipitate particles. In both cases, nickel-filtered copper radiation was utilized. Finally, individual grains of the large-grained castings were examined in the back-reflection Laue geometry. Electron microscope studies were carried out with a J.E.O.L. Model 6A instrument. RESULTS A) Hardness Measurements. Hardness measurements performed at room temperature on the large-grained polycrystalline specimens showed a hardening which was essentially complete in 3 hr. Fig. 1 shows a typical plot of hardness vs aging time. The relative magnitude of the ultimate hardening varied from run to run between 150 and 200 pct of the value for the material immediately after quenching from the solution anneal. Most probably the variations reflect small changes in the time taken to remove the specimen from the vacuum furnace after the solution anneal.

Jan 1, 1969

Jan 1, 1931

By R. H. Edsal, G. Horvay

The transient one-dimensional heat-conduction equation is solved for two semi-infinite media, at different initial temperatures, brought into (poor) thermal contact. It is shown that the two interface temperatures gradually approach the well-known, instantaneously assumed, common interface temperature of the case of zero contact resistance. The present analysis, with slight modifications, may be used in fair approximation also for the class of problems involving a change of phase. One particular application of the boundary value problem solved in this paper concerns the determination of the temerature distribution in metal castings and molds.P This problem has been treated extensively by analytical methods (see e.g., the literature listed in Refs. 1 to 4) by electrical analogs (see e.g., Refs. 11 to 14) and also by experimental methods (see the literature listed in Refs. 4, 5), but prior to the work of Pellini and Ruddle the experimental results were rather unreliable. Immediate motivation for the work described in this paper was to better understand the results of Pellini,' which are typified by the curves of Fig. 1. Pellini cast 20-in. high, 7-in. sq steel ingots into cast-iron molds of various thicknesses. He measured the temperatures at mid-height, at a number of stations in the casting and the mold, and obtained the cooling curves shown in Fig. 1. The most conspicuous thing about Fig. 1 is the large temperature discontinuity at the interface between casting and mold, due presumably to the shrinking away of the casting from the wall and the attendant creation of an airgap, as the casting cools. Such a contact resistance slows down the anticipated freezing rate; an analytical prediction of this is of much interest in foundry practice. The determination of the effect of contact resistance in the presence of a change of phase will be dealt with, by an approximate method, in a separate paper.' In the present paper the much simpler problem is considered in which there is contact resistance but no change of phase. This problem frequently arises in the analysis of aircraft structures.+ It can initial temperature, and may be regarded as semi-infinite. We suppose the thermal properties in the two media to be time, temperature, and space independent; there are no sources or sinks within the media. In Fig. 2(a) we illustrate, schematically, the case of no contact resistance. The semi-infinite media "0" and "2:' initially at temperatures 8 (- m) and 8(+ -), respectively, are brought into contact at time t =0. A common interface temperature 8,i = is instantaneously established, and thereafter remains constant. Temperature curves are drawn for three instants of time. When there is contact resistance between the two media, the temperature equalization occurs as sketched in Fig. 2(b). Fig. 2(c) illustrates a temperature curve, using the dimension-less notation Barber-Weiner-Boley6 have stated the equations [23a, b] given below, which govern the heat transfer in the two media, and solved them for a rather complicated special case. In their example both media "O" and "2" are finite, are insulated at their far ends, and there is steady heat input into medium 2. In Eq. [27] we give the general solution of the most important special case, where the two media are semi-infinite and there are no sources or sinks. In this case the results may be stated in simple closed form. In Fig. 3, to be discussed in the next section, we illustrate the variation of the interface temperature when steel at 2760" is brought into contact with iron at 100". This example, if we disregard the effect of the heat of fusion, is comparable to Pellini's experimental results, Fig. 1. (Unfortunately, however, experimental determination of the interface temperatures was difficult to carry out, and hence Fig. 1 is not very accurate near the interface.) In Figs. 4 and 5 of the following section, we similarly compare Pellini's sandcasting tests with analytical results for the case where steel at 2760" is brought into contact with sand at 100". It will be pointed out that, insofar as the interface temperatures are concerned, heat of fusion has a minor effect, and so the present approximation, with small modifications, may be

Jan 1, 1961

LIEUTENANT MARTIN F. BOWLES Martin F. Bowles, born Apr. 25, 1893, at Bonne Terre, Mo., and graduated from the Neodesha, Kans., High School, had finished all but one month of a four-year course in metallurgical engineering at the Missouri School of Mines, Rolla, Mo., when on May 12, 1917, he entered LIEUTENANT MARTIN F. BOWLES. the first Officers' Training Camp at Fort Riley, Kans. At the close of the training period, he was commissioned a Second Lieutenant and as¬signed to Co. B, 355th Infantry, 89th Division, and stationed at Camp Funston. He left this camp with his company on May 21, 1918, and sailed from an eastern port on June 4, arriving in England on June 15, 1918. After a short stay at a rest camp there, he proceeded to France. On August 14, he wrote that he was with Battalion Headquarters as Scout Officer, 1st Battalion, 355th Infantry, 89th Division. The last letter received from him, dated September 2, was written in his dugout and contained the following: "Here it is 2.45A. M. Sitting in a dugout

Jan 1, 1919