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By Ernest F. Burchard

MOST of the iron ore smelted in Alabama blast furnaces is mined within Alabama, although deposits in the neighboring States of Georgia and Tennessee may be drawn upon when occasion requires. Of the four commercial kinds of iron ore, the anhydrous ferric oxide, hematite (Fe2O3) ; the hydrous ferric oxide, mostly the type commonly known as limonite (2 Fe2O33H2O) ; the carbonate, siderite (FeCO3) ; and the magnetic oxide, magnetite (Fe:3O4) ; the first two are found in abundance in Alabama, the third in less than commercial quantities, and the fourth only rarely. Both the hematite and the hydroxide are found in somewhat different forms according to their geologic environment. The Red Mountain hematite, of Silurian age, that crops out in well¬defined beds for 1.50 miles northeast-southwest and 40 miles northwest-southeast is the predominant source of ore. Only a small part of this area carries ore of commercial value; Birmingham and Gadsden are now the only centers of production. The ore is of sedimentary origin, probably altered from vast deposits of greensand mixed with calcareous, fossiliferous. marine debris. Other types of hematite not vet mined commercially are in metamorphosed rocks-red ore in slates in Columbiana Mountain and specular hematite (gray ore) in quartzite in the Talladega Hills.

Jan 1, 1938

By R. F. Stewart, A. W. Hall

A method has been developed for continuously measuring the moisture content of coal. The method is based on the thermalization of fast neutrons by hydrogen in the coal. Neutrons from a small radio-isotope source penetrate the coal, are scattered by hydrogen, and measured by a thermal neutron detector. The number of thermal neutrons counted can be directly correlated with the moisture content of coal. In a pilot-scale system, moisture was measured continuously within 0.2% in coal moving at rates up to 20 tph. The method is adaptable in industry for continuously measuring the moisture content of coal at high tonnage flow rates. Such an application would permit continuous recording of moisture in coal without sampling and facilitate quality control. An automatic and continuous method of measuring the moisture content of coal is needed by the coal industry. Automatic control of the coal quality would reduce the cost of coal preparation, improve the product, and thus indirectly increase the use of coal. Moisture in coal can be determined by several methods, but the time required to obtain samples and analyze them by existing methods makes it difficult, if not impossible, to control the quality of the product. Both producers and consumers need a method for continuous and instantaneous measurement of moisture content without sampling in order to regulate process equipment and keep the moisture content of coal within specifications. At the Morgantown, W. Va., Coal Research Center we are developing a nuclear method for continuous measurement of moisture in coal. This method is based on the thermalization of fast neutrons by hydrogen in the water and organic matter of coal. Neutrons from a small radioisotope source penetrate the coal, are scattered by hydrogen, and are measured by a thermal neutron detector. The number of thermal neutrons counted can be directly correlated with the moisture content of coal. Design of a moisture meter based on neutron thermalization depends on many variables, any or all of which can affect the sensitivity of the meter. These factors include those related to the nuclear aspect; type and size of neutron flux and source, type of detecting device, and background count; and those related to the coal being tested: rank, particle size, and ash content. A survey was initiated to eliminate the relatively insignificant factors and to ascertain the magnitude of the major effects. Such information was necessary to fully evaluate the technique and to establish design criteria. Coal contains a relatively large amount of hydrogen in the organic coal substance and the water of hy-dration of the shaly material as well as in the moisture. To apply this concept of moisture measurement to coal requires that the organic substance in coal from any one seam of a particular mine be uniform in hydrogen content. The difference in total hydrogen content of wet and dry coal is relatively small, so that a moisture measurement based on this concept requires a measurement between two large numbers to a high degree of precision. Thus, it was necessary to develop a highly precise instrumentation system for continuous measurement and to obtain a physical arrangement permitting measurement of moving coal with a minimum effect from density variation. EXPERIMENT WITH TRAYS OF COAL Tests were conducted with metal trays containing SO to 100 lbs of coal to develop an instrument system of high precision. A scaling system with a maximum instrument error of 0.2% was used to test different types of thermal neutron detectors. The most suitable type of detector was a boron-10-lined proportional counter tube. While this type of detector showed satisfactory stability, extensive testing disclosed a long-term count reduction probably due to some type of deterioration in the detector. However, development of an electronic system using dual detectors eliminated this deterioration as a serious problem. (The second detector would be used to measure a reference drum of dry coal — the difference in count rate between the wet coal and dry reference coal being a direct measure of moisture content.) Table I, column 1, shows typical results with a 1-curie plutonium-beryllium neutron source and a thermal neutron detector beneath a tray of coal and illustrates the precision of measurement. Consecutive measurements (indicated in Table 1, columns 2-5) of thermal neutrons at various times and positions be-

Jan 1, 1968

By D. T. Camp, J. A. Clum

WITH experience, the indexing of back-reflection Laue patterns for cubic crystals is usually a straightforward matter. However, for noncubic systems where in general tables of interplanar angles are not available or when inexperienced personnel are involved, properly indexing a crystal is normally a tedious, time-consuming affair. The authors have written a digital-computer program which calculates and prints out a table of interplanar angles for an arbitrary crystal structure and then systematically searches through this table attempting to obtain a consistent fit to back-reflection Laue data supplied by the user. Of course it is possible simply to calculate a desired set of interplanar angles should this be the only requirement. The program was originally written in ALGOL for use on a Control Data G-21 computer and a preliminary version is described elsewhere.' A version in FORTRAN TV which has been run on an IBM 7040 and one in FORTRAN II run on an IBM 1620 are also available. While it is not the purpose of this communication to describe the program in detail, an indication of how the program operates may help one to decide whether the program would be useful under particular circumstances. The hypothetical example chosen involves the indexing of the zinc crystal which has a hexagonal structure and a c/a ratio of 1.856. Input data for this example consists of only nine cards: The first card controls the list of families of planes to be considered. If the Miller indices of a prospective family are (h k 1), the first digit places a limit, in this case 3, on the absolute values of any individual index. The second digit limits the sum (h +k + l + 1), in this case to 5. Therefore the families (013) and (112) are considered but the family (122) is not. All systems, including the hexagonal, are treated using three-digit Miller indices. The second card contains the crystallographic parameters required to define the system. The first digit is 0 if the system is rectangular, that is all angles are 90 deg. If the system is nonrectangular, as in this example, the digit 1 so indicates. The next three values are the lengths of the sides of the reference cell, a, b, c. The final three entries on the card are the angles, a, 8, y between the sides. The digit 0 on the third card indicates that more data follows, the digit 6 shows that a set of six planes is to be indexed, and the value 2.0 indicates that agreement between a tabulated angle and an input angle is considered adequate if their absolute difference is less than 2 deg. The fourth card lists the measured input angles. a12 = 38 deg, a13 = 24 deg, and so forth. More input angles are listed on cards five to eight with the latter giving the input angle 058 = 40 deg. The final card in this series indicates by the digit 1 that no more data is to be processed. The program operates in the following manner: 1) The input data from cards 1 and 2 is read, thereby indicating the crystal system to be examined and the crystallographic parameters of the particular crystal to be indexed. 2) A table of interplanar angles is generated. 3) The input angles contained on cards 4 to 8 are read. 4) The measured input data is systematically compared with the generated table of standard angles. All combinations of poles whose interplanar angles compare with the requisite, specified accuracy are printed out. If no adequate fit is found an indication of this is printed. A typical line from the generated table of interplanar angles is: (001) - (111) 74.92 64.99 It can be shown that in the Miller-Bravais system the first value corresponds to the angles between (0001)-(1121) and the second to that between (0001)-(1011). This particular set of data gave the following result for the planes 1 to 6: (011) (110) (121) (111) (112) (010) The ALGOL version also has the option of simply providing the Greninger-chart coordinates ? and 6

Jan 1, 1967

By M. C. Flemings, A. A. Tzavaras

Analytical and experimental procedures are descrihed for quantitative determination of volume-fraction microporosity in metals by mimorarlio-graphg. The analysis assumes spherical pores but allows for the observed fact that pores or portions of pores smaller than a given thickness do not project an image on the film. Volume-fraction microporosity was measuured in cast low-alloy steel and shown to vary from 0.6 x 10-4 to 10 x 10 depending on mode of solidification and on whether the material was air- or vacuum-cast. The aim of work described herein was to develop a method of quantitative measurement of the volume fraction of microporosity in cast metals. Microporosity, present in nearly all castings and ingots, is always interdendritic in nature and may be large enough to be seen on a polished surface with the naked eye. More generally, it is smaller in size, and its detection more difficult. Three techniques might be considered for measurement of microporosity: 1) lineal analysis of a polished metallographic surface, 2) density measurement, or 3) quantitative microradiography. As will be shown later, volume fractions of porosity in directionally solidified castings may be the order of 10-4 to 10-3; such small amounts of porosity are difficult to identify and measure on a polished surface. Density measurement is also not a suitable technique (for alloys) when the volume fraction of porosity is low. This is because the density of the base metal is often not known within the necessary accuracy, due to microsegregation or partial phase transformations. In general, it is not possible to completely eliminate microsegregation without also altering the porosity. Because of the limitations of the foregoing techniques, quantitative microradiography was employed to determine amount of porosity. In recent work, microradiography has been found to be useful for qualitative measurement of porosity, including determination of size and shape of individual pores;&apos;)&apos; however, quantitative determination of amount of porosity has not been attempted. I) CALCULATION OF VOLUME-FRACTION POROSITY The following analysis employs procedures similar to those of Cahn and Nutting3 and Hilliard.4 Major simplifications are that pores are assumed to be spherical and to be present in sufficiently small quantities that no overlapping occurs. A basic difference from the previous treatments is that the limited "sensitivity" of microradiography is considered. Assume first 1) cavities are spherical and of uniform diameter, 2) cavities are randomly distributed, 3) volume-fraction porosity and specimen thickness to pore radius ratio are sufficiently small that overlapping of the projected images of cavities is negligible, 4) sensitivity is limited (i.e., holes or portions of holes of less than a given thickness do not project an image on the film). The sensitivity, is defined as: where 5 = minimum thickness of void from which an image will be projected on the film and t = specimen thickness. Now, from Fig. 1, it is possible to distinguish between two different types of holes. These are 1) holes whose centers lie within the region t/2 > X > 6/2, where X is distance from one surface of the specimen (positive into the specimen), and 2) holes whose centers lie within the region (6 — r) < X < 6/2, Holes whose centers lie outside X = (6 -r) project no image on the film. These two types of pores are considered separately below. Type 1 Pores. When 6 is greater than 0, the image of a spherical cavity of radius r appears on the film as a circle of radius a which is smaller than r. From geometry, Fig. 1: a2=r2-52/4 [2] where a = radius of image of pore on film and r = radius of pore. Since the pores are randomly distributed and spherical V =4/3pr2Nv [3] where V = volume fraction of voids and Nv = number of pores per unit volume and the number of images of Type 1 pores per unit area of film, N&apos;A, is

Jan 1, 1965

By B. R. Hollebone

The chemical action of molten anhydrous pyridinium chloride (pyridine hydrochloride) on oxy salts and ores of some Group IV and V metals are discussed-in particular zirconium, hafnium, niobium (columbium) , and tantalum. Laboratory-scale experiments are described whose results suggest that this reaction might provide a practicable means of converting ores of these metals to the anhydrous metal chlorides. Experimental results are given which provide some insight into the nature of the reactions and some of the compounds which could be present at intermediate stages. The treatment of ores of the more refractory metals is difficult and expensive and often demands the use of gaseous chlorine, hydrogen fluoride, or other reagents which are, if nothing else, expensive and dangerous to use. This situation is, of course, due to the strong metal-oxygen affinity resulting from the high charge and the small size of the metal ion which combine to produce such high lattice energy in the metal oxide as to defeat standard reduction methods. Thus, the characteristic of these metals which leads to one of their most important properties—corrosion resistance—is the main hurdle in obtaining the metal. Many common methods&apos; for treating ores of zirconium and niobium (columbium), for example, proceed as directly as possible to the preparation of anhydrous halides. These halides are purified by now standard processes of solvent extraction, fractional distillation, and so on. This paper reports on preliminary stages in the development of a method of treating these ores—particularly of niobium—so as to prepare the anhydrous, volatile halides by the use of chemical reagents which are much more easily handled than those used at present. CHEMICAL PRINCIPLES The solvent action of aminium halides has been referred to periodically in the literature over several decades. The chemistry of pyridinium chloride has been discussed particularly by Audreith2 and Starke.3 However, since this is not familiar chemistry in its nonaqueous setting, it is perhaps well to point out some general metallurgical principles and applications. One can use, as point of departure, the fact that HC1 dissolved in pyridine is an acid very much the same as aqueous HC1. It thus gives essentially all the reactions of the HC1 with which we are familiar. However, when the ratio of HC1:pyridine reaches 1:l (a ratio far higher than is possible with H2O) the solution becomes solid C5F5NHC1, pyridinium chloride.* Inter- estingly, the acidic properties of HC1 persist in this medium, although they are manifest only in the molten state of the compound. Some typical reactions of divalent metal compounds which we have carried out in our laboratories are the following: 2PyHCl + Zn — (ZnCl2) + H2 + 2Py 2PyHCl + MnO — (MnCl2) + H2O + 2Py 2PyHCl + CuS — (CuCl2) + H2S + 2Py 2PyHCl + CaCO3 — (CaCl2) + H2O + CO2 + 2Py In these equations, the parentheses indicate a solvated compound which in water would be predominantly a hydra ted cation but which in molten PyHCl will more likely be a complex chloro-anion of the type MC14-. Some important physical properties of pyridinium chloride (PyHCl) are given in Table I. One sees from the data in Table I that at the temperature of molten pyridinium chloride both water and pyridine will boil away. Thus the system will be kept anhydrous. For this reason the reaction 2NbCl5 + 5H2O— Nb2O5 + 10HC1 has no counterpart in molten PyHCl. Instead, the chloride is made even more stable by the formation of a hexachloro complex: Nb2O5 + 12PyHC1 — 2PyHNbC16 + 5H2O + 10Py One interesting property of these complexes is their thermal instability which for the case of niobium can be illustrated as PyHNbCl6 — PyHCl + NbCl5 With a view to possible use of this chemistry in ore treatment, we have attempted to dissolve Pyrochlore (essentially FeO - Nb2O5) and recover the NbC15 from it.

Jan 1, 1968

By P. Chaudhari, Michael B. Bever

The heat of solution at infinite dilution of selenium in bismuth, the heat of mixing of selenium and bismuth, and the limit of solubility of selenium in bis~rzuth have been determined at 573, 623; and 663°K by metal solution calorimetry. The heat of forrrzation of the compound Bi2Se at these temperatures has been determined from the heat effects associated with the precipitation of the compound from a saturated solution oj selenium and bismuth. The published information on the thermodynamic properties of the system Bi-Se is limited. The heat of solution at infinite dilution of selenium in bismuth at 623°K has been measured.&apos; The heat of formation at 273 K1 and room temperature2 and the heat capacity at 80 K3 of the compound Bi2Se3 have been reported. An estimate of the heat of formation of the compound BiSe at room temperature has been published.2 Information on the phase relations in the system Bi-Se is available.&apos; In the investigation reported here the following quantities have been determined at 573", 623", and 663°K: 1) the heat of solution at infinite dilution of selenium in bismuth, 2) the heat of mixing of selenium and bismuth in bismuth-rich solutions, 3) the limit of solubility of selenium in bismuth, and 4) the heat of formation of the compound BizSe. These quantities were determined by the addition of selenium to bismuth-rich solutions in a metal solution calorimeter. The determination of the heat of formation at the tem- perature of the calorimeter bath involved the precipitation of the compound from a saturated solution in the calorimeter. 5,6 This method differs from that commonly used which requires the addition of the compound and of a mechanical mixture of its components and yields the heat of formation at the temperature from which the additions are made (273 K EXPERIMENTAL PROCEDURE AND CALCULATIONS The solution calorimeter has been described in detail.&apos; Pure bismuth (99.999+ pct) was used as the bath at the start of a run. The calorimeter was calibrated with small amounts of bismuth added from 273°K; the differences of the heat contents of bismuth at 273°K and the temperatures of the baths are listed in Table I. After the calibration, additions of hexagonal selenium (99.999+ pct) were made. Loss of selenium by evaporation was negligible. No unusual experimental difficulties were encountered.9 The differences in the heat contents10 of selenium at 273°K and the temperature of the bath, listed in Table I, were subtracted from the measured heat effects to give the "adjusted heat effects". The methods by which the heat of solution at infinite dilution, the

Jan 1, 1968

By N. Mungan

A study was made of the effects of wettability and interfacial tension on the immiscible displacement of a Iiquid by another Iiquid from porous media. The influence of viscosity ratio was also investigated. Porous media used were polytetrafluoroethylene (TFE) cores prepared by compressing TFE powder under different pressures. lt is shown that displacement of a wetting by a nonwetting Iiquid is always less efficient than the displacement of a nonwetting by a wetting fluid, all other things being equal. In the former case, the recovery efficiency can be increased substantially by either reducing the interfacial tension or increasing the viscosity of the displacing fluid. A qualitative discussion is given on the implications of this work to the recovery of crude oil by water flooding. INTRODUCTION The high cost of oil exploration and new recovery schemes makes it imperative that waterflooding be conducted under conditions favoring most efficient oil recovery. To improve oil recovery by waterflooding, it is essential that the role played by interfacial forces in the entrapment of residual oil be studied and understood. Interfacial phenomena in natural rock, connate water and crude oil systems are very complicated because of the complexity of the natural liquids found in petroleum reservoirs, because of our inability to adequately describe the geometrical structure of the porous media and because of a lack of understanding of physical and chemical interactions between the liquids and surface of the pores. The problem becomes further complicated when one tries to elucidate the role of interfacial phenomena in fluid flow. Numerous studies of the displacement of oil by water under different interfacial tension or wet-tability conditions have been made.lm3 These studies have been performed in silica, alundum or sandstone systems using water and paraffin oil and also some surface active material to control the interfacial tension s and the contact angle 0. Unfortunately, the high energies of various interfaces involved favor adsorption and orientation of the surface active material at the interfaces. Also the surface active material concentration at the interfaces exceeds that in the bulk of the liquid phases. Such surface excess may cause the surfactant distribution, the contact angle and the interfacial tension to differ from their measured static equilibrium values and makes interpretation of the displacement experiments difficult. Furthermore, as changes in s also lead to changes in cos 0, the role played individually by one of these parameters in the displacement becomes obscured by the effect of the other. To circumvent these difficulties, a low surface energy solid and true solutions or pure liquids should be used. Use of a low surface energy solid minimizes adsorption and orientation effects at the solid-liquid interfaces. By controlling s and cos 0 through use of selected pairs of pure liquids or true solutions rather than by surfactants, the adsorption effects at liquid-liquid interfaces are eliminated. In the present study TFE cores were used as the porous media. Liquids used were water, sucrose solutions, paraffin oils and benzyl, n-butyl and isobutyl alcohols. The interfacial tension was varied from 40 to 1.1 dynes/cm by suitably choosing the liquid pair. A surface active material was added to the water-oil system only in the case where interfacial tension of 0.5 dyne/ cm was desired. No precise changes of cos 0 were attempted. However, either the displaced or the displacing liquid could be made the one which preferentially wets the TFE surface. Using sucrose solutions and blends of paraffin oils proved to be a convenient way of changing the viscosity ratio between the displaced and displacing liquids. The present investigation examines the effect of interfacial tension, wettability and viscosity ratio on the immiscible liquid-liquid displacement from porous media. Observed data permit a

Jan 1, 1967

By J. J. Bowman

The term "secondary aluminum" frequently is used loosely and often is considered synonomous with "inferior quality." Under war conditions, when every pound of material must contribute its share to the job at hand, this type of thinking is most unfortunate. Actually, given a supply of segregated scrap, an experienced smelter can produce remelted ingot of good quality, comparing closely to the analysis of the original material, and of considerable value of the war effort. The alloys he can produce are, of course, somewhat controlled by the analysis of the available scrap and, by the very nature of things, some of his production is not suitable for indiscriminate use. However, remelted scrap ingot provided about 273,2 per cent of this country&apos;s domestically-produced 1942 aluminum supply and probably will comprise about 39 per cent of the 1943 supply. (Canadian production is excluded from these figures.) That this part of the supply remains important is indicated by a recent report that "requirements" for the second quarter of this year were about 14 per cent greater than the supply, even though that supply will be almost twice the prewar annual production. (And those requirements, incidentally, were prepared after many conservation measures had been taken into account.) Since W. Bonsack recently has published a paper2 on the effects of the various alloying elements and impurities on the properties of aluminum, and such con¬siderations really are the important ones in a discussion of the metallurgy of secondary aluminum, it is planned to restrict this discussion more to a consideration of the sources, general characteristics and possible uses of these materials. For the purpose of this discussion, mill (or run-around) scrap may be disregarded and only plant scrap and obsolete scrap considered. Plant scrap, of course, is that scrap which is generated during the production of some part or assembly from a fabricated form of aluminum, such as sheet, tubing, forgings, castings or the like, and it may consist of solids (including rejected parts or subassemblies) or of machinings. To the extent that the several alloys are effectively segregated and the material is properly identified, the composition after remelting can be rather closely controlled or predicted. Obsolete scrap, on the other hand, is the "junk" which accumulates because of the wearing out or breakage of some piece of equipment. Although it is almost always in the form of solids, the accumulation includes many different alloys (often in the same assembly) and may include a considerable amount of nonaluminum material. The "metallics" recovered from drosses also contribute a portion of this class of material. The composition after remelting, therefore, may vary over rather wide limits and can not be very accurately predicted in any specific instance. SEGREGATION OF PLANT SCRAP Unfortunately, perhaps, it was not very common practice before the war to

Jan 1, 1943

By Benjamin F. Tillson

Although portable fire extinguishers are valuable for fires in an incipient stage, some medium that will dissipate a large amount of heat is needed to fight a fire in mine timbers, because of the size to which the fire will probably have grown before it is discovered. Scaling off, or otherwise smothering such a fire with gases that will not support combustion, is often ineffective for the residual heat will cause reignition when the area is opened and fresh air reaches the hot charred timber. The most effective ways of fighting mine fires, therefore, are to drown and cool the hot zone with water, and to "load out" the partly burned material. Either of these methods requires a direct attack of water ; upon the inflamed material; therefore, every mine containing a large &apos; quantity of timber or other combustible should be as completely equipped with a fire-hydrant system as it is with compressed-air mains. Mine managers may object to the expenditure, especially if they have not suffered from mine fires. The cost of such preventative measures, however, is only a small portion of the possible losses, and the water pipes can be used for other purposes, which will pay the carrying charges. They can supply water to the rock drills, which will encourage more wet drilling with hollow-drill steel, for the trouble and expense of packing water to individual tanks at the drills will be removed. The carbon-tetrachloride hand extinguishers seem to have no place in mining except for fires that start in electrical equipment. They give off noxious gas, which may prove poisonous in confined quarters; and as it is heavier than air it is of no value for smothering fires overhead or in side timbers and would be dissipated by a good ventilating draft. The old soda-acid extinguisher or the more modern "foam" types &apos; are preferable. The former probably does not rely for its efficacy on the carbon dioxide generated but on the smothering and cooling effect of the water and the trajectory of stream that may be obtained because of the gas pressure developed. The production of a foam having a tough film to smother a fire, even on overhead surfaces, with the added

Jan 1, 1923

By Benjamin F. Tillson

Although portable fire extinguishers are valuable for fires in an incipient stage, some medium that will dissipate a large amount of heat is needed to fight a fire in mine timbers, because of the size to which the fire will probably have grown before it is discovered. Scaling off, or otherwise smothering such a fire with gases that will not support combustion, is often ineffective for the residual heat will cause reignition when the area is opened and fresh air reaches the hot charred timber. The most effective ways of fighting mine fires, therefore, are to drown and cool the hot zone with water, and to "load out" the partly burned material. Either of these methods requires a direct attack of water ; upon the inflamed material; therefore, every mine containing a large &apos; quantity of timber or other combustible should be as completely equipped with a fire-hydrant system as it is with compressed-air mains. Mine managers may object to the expenditure, especially if they have not suffered from mine fires. The cost of such preventative measures, however, is only a small portion of the possible losses, and the water pipes can be used for other purposes, which will pay the carrying charges. They can supply water to the rock drills, which will encourage more wet drilling with hollow-drill steel, for the trouble and expense of packing water to individual tanks at the drills will be removed. The carbon-tetrachloride hand extinguishers seem to have no place in mining except for fires that start in electrical equipment. They give off noxious gas, which may prove poisonous in confined quarters; and as it is heavier than air it is of no value for smothering fires overhead or in side timbers and would be dissipated by a good ventilating draft. The old soda-acid extinguisher or the more modern "foam" types &apos; are preferable. The former probably does not rely for its efficacy on the carbon dioxide generated but on the smothering and cooling effect of the water and the trajectory of stream that may be obtained because of the gas pressure developed. The production of a foam having a tough film to smother a fire, even on overhead surfaces, with the added

Jan 1, 1923

By D. A. Dukelow, K. Li, G. C. Smith

Decarburization in the Fe-C system by oxygen top blowing has been studied in laboratory -scale experiments. It is shown that equilibrium models fail to explain or predict either the course of refining or endpoint conditions, giving results which either are incompatible with the chemistry of the system or do not satisfy material balance requirements. Also the path of decarburization was found to vary even for heats made under apparently identica1 conditions. A promising approach to analyzing the decarburization results is to relate oxygen efficiency fm carbon removal to bath carbon content. This relationship for Fe-C heats shows the same range of oxygen efficiencies as is obtained in pilot-plant and commercial heats using hot metal-scrap charges. This implies that oxygen transfer is primarily controlled by the decarburization reaction itself, independent of other refining reactions. Therefore, it should be possible to study separately decarburization and slag-metal reactions. DECARBURIZATION is probably the most important reaction in steelmaking. Not only is it a main reaction in the refining of iron to steel but it also provides the stirring action in the bath necessary for the diffusion processes to proceed at reasonable rates so as to make a steelmaking process practical. Kinetics of decarburization in the open-hearth process has been a subject of investigation for many years.&apos;-B It is generally accepted that at steelmaking temperatures the rate of homogeneous C-0 reaction is extremely high and cannot constitute a rate-controlling step. Diffusion of oxygen through a boundary film in the metal phase has been suggested by arken&apos; as rate-determining. Recently, Larsen and sordah16 concluded from experiments in a laboratory furnace that, with oxygen supplied from air or combustion gases, the rate of "steady-state" carbon boil is controlled essentially by a diffusion process of O2, Co2, or H2O through a film of nitrogen above the slag surface. Displacing this diffusion film by a stream of nearly pure oxygen produced a ten-fold increase in the rate of carbon boil with the rates of slag-metal oxygen transfer, bubble nucle-ation, and other steps all apparently able to keep pace. In the top-blown basic oxygen process, however, the transport of oxygen takes a more direct route. and the state of bath agitation is much more turbulent than in the open-hearth process. In addition, direct contact of the gas with the metal phase provides opportunity for direct oxidation of carbon. It is likely that the rate-limiting factor for the decarburization reaction will be different. However, only a few descriptive discussions of the subject have been reported in the literature.10-l2 Studies of the decarburization kinetics based on plant or pilot-plant data are necessarily complicated and are influenced by other refining reactions which occur simultaneously. In order to investigate the mechanism of decarburization, experiments have been conducted in which carbon-saturated iron melts were top-blown with pure oxygen over a range of conditions. It is hoped that this study will form a foundation on which a more basic understanding of this important reaction may be built. EXPERIMENTS One group of blowing experiments was made in a standard 200-lb induction furnace and another group in a 500-lb induction furnace. The furnaces were modified to the general shape of a basic oxygen furnace by adding a rammed refractory cone section to the regular crucible body. Crucible and cone were of high MgO (95 pct) material. A water-cooled lance, 1/2 in. in diam and threaded at one end to take a nozzle, was used for blowing oxygen. The lance with its water and oxygen lines was supported on a cantilever arrangement so that it could be moved up, down, or sideways. Oxygen of 99.5 pct purity was supplied from a cylinder and metered through a rotameter equipped with pressure and temperature gages. Another pressure gage was located at the top of the lance. A schematic diagram of the assembly is shown in Fig. 1. Before each experiment, a weighed amount of ingot iron, containing 0.02 pct C, < 0.01 pct Si, 0.10 pct Mn, 0.019 pct P, and 0.015 pct S, was charged in the furnace and melted down by induction heating. Graphite was then added to the molten charge until it became saturated. When the temperature of the charge reached the desired level, the lance was lowered to a predetermined height above the bath

Jan 1, 1964

By W. C. Hauber

Techniques previously published to predict the production performance of a water flood when the mobility ratio is not unity have been primarily restricted to a five-spot well pattern. When other types of well patterns are considered, the prediction of performance has required either a model study or a complex numerical solution of a multiple-fluid system with a high-speed digital computer. Simple methods are developed in this report for predicting the areal sweep efficiency and injectivity history of a water flood for arbitrary well patterns and mobility ratios. The effect of an initial gas saturation can be incorporated into this method of prediction. With the layer superposition concepts published by Prats, et al.,1 these methods can be used to predict the production performance of a water flood in a reservoir having a wide range in permeability. A reasonably good agreement is shown by comparisons of the results calculated by this method with those obtained either by model studies or by complex numerical solution of multiple-fluid systems. Therefore, it has been concluded that a reasonably accurate method has been developed for predicting the production performance of a water flood employing an arbitrary type of well pattern for any given mobility ratio. A medium-speed digital computer can be used in applying this method. INTRODUCTION Production performance of multi-fluid five-spot water floods can be predicted by the techniques published by Prats, et al.1 This technique takes into account the effects of initial gas saturation, mobility ratio and vertical variations in horizontal permeability. A basic assumption in applying this technique is that unit displacement efficiency does not vary with time after the passage of the flood front. Prats, et al. demonstrated that this assumption is valid for normal waterflood applications with small mobility ratios. To extend Prats&apos; technique to other types of well patterns has required either an experimental model study or a numerical solution of a multiple-fluid system to describe the performance of an individual homogeneous layer. Sheldon and Dougherty2 presented an exact numerical solution employing any arbitrary well pattern. This technique is complex to apply, requiring (1) numerical solution of the single-fluid system, (2) conformal mapping of the streamlines and iso-potential lines to form a new grid network, and (3) a numerical solution of the multi-fluid system on the new grid network. A method was developed in this paper to approximate areal sweep efficiency and injectivity as functions of time for an individual homogeneous layer for arbitrary well patterns and mobility ratios. Analytic expressions were derived to directly apply this method to five-spot and direct line drive well patterns. For other types of well patterns, this method is similar to the approach of Higgids and Leighton,6 in that it utilizes the stream tubes and iso-potential lines obtained by the solution of differential equations when the mobility ratio is unity. However, this method is easier to apply than the Higgins-Leighton method since it does not require knowledge of the variation between oil and water relative permeabilities and saturation. Using the relationship between areal sweep efficiency, injectivity and the volume of water injected into an individual homogeneous layer as obtained by the method presented in this paper, and Prats&apos; technique for the superposition of individual layers, one can predict the production performance of any water flood. ASSUMPTIONS GENERAL Basic assumptions made in this report are that fluids are incompressible and the layers are horizontal, homogeneous and uniformly thick. It is assumed that as water is injected into the layer, three distinct regions are formed —a water bank, an oil bank, and an unflooded region. Each region is assumed to displace other regions in a pis-tonlike manner, with only one fluid flowing in each region, so that there is no change in unit displacement efficiency with time after the flood front has passed in the reservoir. Therefore, the residual oil saturation in the water bank and the oil saturations in the unflooded region are constant throughout the layer. The ratio (F) of the bulk volume of a layer occupied by the oil and water banks at any time before oil breakthrough, to the corresponding bulk volume of a layer occupied by the water bank, is given&apos; by the equation BREAKTHROUGH AREAL SWEEP EFFICIENCY To predict the behavior of any type of waterflood pattern, one must know the breakthrough areal sweep efficiency Eb(Mc,o, F) for the pattern for any water:oil mo-

Jan 1, 1965

By Nathaniel Arbiter

THE separation of minerals by flotation can be regarded as a rate process, with the extraction of any one mineral determined by its flotation rate, and the grade of concentrate by the relative rates for all the minerals. So regarded, the significant variables for the process are those that control the rates. These variables are of two types, the first describing the ore and its physical and chemical treatment prior to flotation and the second characterizing the separation process in the cells. This paper will examine the variation in rates for a group of separations, will show that a simple rate law appears to govern, and will consider the relation of the control variables to the rates. The use of rate constants for evaluation of performance and efficiency will be discussed. Flotation involves the selective levitation of mineral and its transfer from cell to launder. The flotation rate is the rate of this transfer. It may be defined by the slope of a recovery-time curve for any cell in a bank, or at any time in batch operation. The objective in flotation rate study is an equation expressing the rate in terms of some measurable property of the pulp. This can be either the concentration of floatable mineral in weight per unit volume1,2 or a relative concentration, which will be a function of the recovery." A rate equation for an actual flotation pulp will contain at least two constants, both to be determined from the data. One of these, the initial concentration or proportion of floatable mineral, is not necessarily equal to the feed assay because of nonfloatable oversize or locked particles." The other, a rate constant, is a measure of proportionality between the rate and the pulp property on which the rate depends. The value of the rate constant will be determined by the values of all variables which control the process and will be changed by significant changes in any of them. It is, therefore, a direct measure of performance. Where recovery or grade change continuously with flotation time, the rate constant will be independent of time and will characterize the entire course of the separation. Development of Rate Equations Rate equations can be developed either by analysis of the mechanism of the process or by direct fitting of equations to recovery-time data. Sutherland&apos;s attempt by the first method&apos; suggests that the effect of particle size variation on the rate complicates the derivation of a simple equation applicable to an ore pulp. A further problem with an ore is the concentrate grade requirement, which usually involves a variable rate of froth removal. Thus the final rate for any cell may depend on the froth character and froth height, as well as on the pulp composition. This does not imply that each cell cannot reach a steady state2 in which the rate will depend ultimately on pulp composition. The second method is the fitting of rate equations consistent with the necessary boundary conditions* to experimental recovery-time curves. On the assumption that under constant operating conditions the flotation rate is proportional to the actual or relative concentration of floatable mineral in the pulp, a generalized rate equation may be expressed as follows: Rate = Kcn [I] where K is the rate constant, c is some measure of the quantity of floatable mineral in the pulp at time t, and n is a positive number. In previous rate studies, the value of n has been taken as 1, either by direct assumption," or as a result of the hypothesis that bubble-particle collision is rate determining.&apos; A first order equation results, which after integration in terms of cumulative recovery R, leads to Loge A/A-R = Kt [2] The quantity A is the maximum possible recovery with prolonged time under the conditions used. No conclusive proof for the validity of this equation in flotation has been advanced. The evidence cited in its support consists entirely in the demonstration that it appears to apply to a limited number of recovery-time curves."&apos; It will be shown subsequently that this procedure is not sufficient to establish the order of a flotation rate equation. The possibility that the equation may be of higher order therefore requires examination. If, in particular, the exponent in eq 1 is assumed to be 2, then after integration there results R = A2Kt/1 + AKt [3] with K again a rate constant and A the maximum proportion of recoverable mineral. Eq 3 may be

Jan 1, 1952

By D. W. Loucks

There is plenty of evidence to indi-cate that at least one of man&apos;s chief interests in life is to make himself as comfortable as possible. If you doubt this, just watch the fellow next to you for the next half hour trying to find the most comfortable position that a hard chair has to offer. Comfort, however, does not always mean an easy chair. To some, it may mean a wealth of money; to another, freedom from worry. But to most of us, it means first of all a comfortable atmosphere in which to live, and to a great many of us it probably also means freedom from that annoying task of firing the furnace. Today more than ever before. automatic heat is one improvement that is placed high on everyone&apos;s list. Perhaps this is because automatic heating is becoming relatively cheaper. Perhaps it is because of a good publicity campaign on the part of the oil and gas men or maybe it is just that we are getting lazier day by day. At any rate, almost every issue of Better Homes and Gardens, House Beautiful, or your other favorite home magazine carries an article extolling the virtues of this or that automatic heating system. If I were to ask you to name the first thing that came to your mind when I said automatic heat, you would prob-ably say either gas furnace or oil burner. Or if you had just been studying heating systems, you might possibly say heat pump. But chances are you would not mention anything about coal, and yet coal is the most common source of the greatest automatic heat of them all. I say this because coal is the fuel used almost universally by the district heating industry in producing and delivering to certain heavily populated areas heat ready to use at the touch of a valve or the click of a thermostat. Although the industry is over a half century old, it has not experienced the widespread development of other utility industries because of certain limitations which I believe you will realize from the next few minutes discussion. District Heating Operations We may define district heating as any operation where two or more buildings are heated from a central heating plant. The method of heat transfer may be hot water or in some cases warm air, but generally the medium of heat transfer is steam. So universally is steam used that the industry is frequently referred to as the district steam industry. The Allegheny County Steam Heating Co. which operates the district heating system in downtown Pittsburgh is a subsidiary of the Du-quesne Light Co. Although organized in 1912 primarily as a means of securing the electric load of downtown buildings, the service has now become so valuable and so popular that it is no longer considered a necessary adjunct to the electric business but rather a separate business standing on its own feet. Fig 1 shows the layout of the plants and distribution system of downtown Pittsburgh. Two generating plants, one known as the Stanwix and the other as Twelfth Street, supply the area. Each has two boilers with capacity totaling 1,350,000 lb per hour. The Stanwix Plant is supplied coal by truck. The coal is pulverized at the plant and burned as powdered fuel. Coal is supplied to the Twelfth Street Plant also by truck but the boilers arc stoker fired. Over 1 1/2 miles of tunnel house a portion of our main lines, but it requires over twelve miles of pipeline, ranging in size from 32 down to 1 in. in diameter, to supply all our customers. The distribution system consists of two systems in a sense, one high and one low pressure with certain interconnections between the two. Our high pressure system supplies steam up to 125 Ib to some but not all customers, while the low pressure system operates in the range of 10 to 20 psi. Note that the two plants are tied together through large steam mains and that the system to some extent is a loop system, making it possible to have a portion of the line shut, down without interrupting service to any customer. Fig 2 conveys a picture of the extent to which steam service is used in the downtown triangle. The black area indicates the buildings which now use district steam. The dotted area indi-

Jan 1, 1950

By J. C. Holm

ALTHOUGH the main constituents of Portland cement are the oxides of calcium, silicon, aluminum, and iron, characteristics of the cement are seriously affected by such contaminants in the raw materials as magnesium, phosphorus, sodium, potassium, sulfur, and others of lesser importance. Sources of cement raw materials comprise a long list of minerals occurring in nature in various degrees of purity. The calcareous raw materials are generally limestone of purity varying from calcite to cement rock (a low-grade limestone of natural, almost correct chemical composition), chalk, marl, seashells, coral, and coral sand. The argillaceous raw materials supplying silicon, aluminum, and iron are mainly various forms of clay and shale, to which may be added silicious sand, iron ore, bauxite, or kaolin for minor adjustment of the chemical composition. The quality of Portland cement in this country, as in most parts of the world, is controlled by rigid specifications limiting both its chemical and physical characteristics, and cement manufacturers must comply with these specifications to market their products. Brandon Raw Materials: An unusual deposit of marl, limestone, and clay occurs 12 miles east of Jackson, Miss., near the village of Brandon. The deposit is of sedimentary origin and of relatively young geological age. Layers of marl vary from putty-like consistency to such hardness that it can be cut with a knife. Interspersed between the layers of marl are bands of limestone varying from very soft to hard. the compressive strength of the hardest layers exceeding 15,000 lb per sq in. The layers of marl range in thickness from a few inches to about 25 ft. The limestone bands seldom exceed 2 to 3 ft but often occur in thinner veins in the quarry face. Above the top layer of the deposit, which may be marl or limestone, a layer of clay ranges in thickness from a few inches to more than 20 ft. Part of this clay is harvested with the raw material to supply part of the argillaceous components, but most of it is stripped as overburden and wasted. A highly silicious clay of extreme fineness, harvested from the bottom of the quarry below the marl and limestone bands, is to correct the silica content. Fig. 1 shows typical examples of the interrelation of the various materials, based on drill logs obtained during exploration of the deposit. The marls vary in moisture content in the bank from 15 to 30 pct and contain up to 70 pct -200 mesh particles and up to 40 pct —10 p particles. A large percentage of the fine fraction is within the colloidal range, making the marl extremely sticky. The limestone beds range in hardness from that of the hardest marl to a medium hard limestone and in moisture content from 2 pct to approximately 14 pct. The line of demarcation is often difficult to draw and the moisture content is possibly the best means of classification. The ratio of soft to hard material is not constant throughout the deposit, but the average is approximately 70 pct soft to 30 pct hard material. Through the years this deposit had been repeatedly explored by cement companies and rejected as unsuitable for cement manufacture, mainly because of physical characteristics. In 1950, after careful exploration of the deposit and comprehensive laboratory and pilot plant tests of the raw materials, officials of Marquette Cement Mfg. Co. of Chicago were convinced that a practical and economical method of processing the raw materials had been devised and authorized construction of a new plant that began production in December 1951. Marl and limestone, common raw materials for Portland cement, usually occur in such a manner that they can be worked separately. Their harvesting and processing normally have presented no difficult problems, as standard equipment and methods are available for handling either sticky or hard materials. No other cement plant utilizes a deposit of the nature of that at Brandon, however, and for this reason no prior art was available for design. When properly blended, the raw materials produced an excellent cement without additives. Basic problems to be solved in designing the cement plant were:

Jan 1, 1957

By J. J. Kramer, W. A. Tiller, G. F. Bolling

The solidification of poly crystalline zone-refined lead has been examined. A novel casting technique was used, with several advantages such as unidirectional heat flow, atmosphere control, and decanting of the liquid during any stage of growth. The experimental results show the separate existence of two textures, a (111) surface texture at the chill surface and a texture in the columnar zone, in the absence of conditions which would produce dendritic growth. WALTON and chalmers have most recently shown that the dendrite direction is the preferred axial orientation for the solidification of many metals in casting. Experimentally, for aluminum and lead, they showed that in the columnar zone the dendrite direction, <l00>, predominated, developing from an equiaxed chill cast layer that exhibited no preferred orientation. A reasonable description of the way in which grains closer to the dendrite orientation were able to encompass other grains was then set forth. For their materials, it was also shown that high superheats could inhibit a preferred axial orientation from developing, presumably by inhibiting dendrite growth. The observations of Rosenberg and iller, on the other hand, showed that zone-refined lead, cast under conditions similar to those of Walton and halmers,&apos; had a definite <111> texture in the columnar zone. However, no examination was made of the chill surface to find out if the columnar zone texture was independent of the orientations at the surface. Since the existence of preferred growth in Upure" lead is thus in doubt, a reexamination of the casting of zone-refined lead is presented here, using a novel casting technique. EXPERIMENTAL PROCEDURES AND RESULTS Zone-refined lead was prepared from two starting materials;99.999+pct supplied by ASARCO, and 99.999pct supplied by COMINCO. The manner of zone-refining and the phenomenological tests for purity after refining, have been describedelsewhere.&apos; The casting apparatus is shown schematically in Fig. 1. The following general procedure was used: The metal was cut directly from the best parts of

Jan 1, 1963

By C. D. Dolman

Since the outbreak of the war we have discovered in the united States minerals of which there was no general knowledge, and which compared very favorably with anything that could be found in any foreign country. One of these was magnesite, or the carbonate of magnesium as it occurs in nature. This mineral crystallizes in the rhombohedra1 form, has a specific gravity of 3.00, molecular weight of 84.4, molecular volume of 28.1, and a hardness of 3.5 to 4.5.1 Had it not been for the development of the California deposits of this mineral and the discovery of immense new deposits in Stevens County, Wash., the production of steel during the war would have been more seriously handicapped than it was. Now that the war is over, we face the possibility of competition with the cheap Austro-Hungarian magnesite; and while that may not be so cheap as it was before the war, adequate protection should be given the producers in this country to insure the full development of our own resources. The consumption of magnesite in the United States in 1913, the year preceding the war, was 172,591 tons of calcined and 22,872 tons of crude magnesite. Less than 3 per cent. of this amount was produced at home. At the present time, practically all of the magnesite used in the United States is produced at home. Expensive plants have been constructed, extensive exploration work done, and production pushed to the utmost to supply the necessary requirements of the war. Thus a considerable industry has been built up within our borders. Some magnesite has been imported from Canada and Mexico, but the Canadian ore was of an inferior grade and could not be used satisfactorily. During the year 1918, production decreased in both the United States and Canada; the production in the United States was 225,000 tons in 1918 as against 315,000 in 1917, and in Canada 39,365 tons in 1918 as against 58,090 in 1917. This decrease was mainly due to over-production during 1917, the domestic demand being only 300,000 tons. The material produced and sold in the United States must contain, in the crude form, not more than 3.5 per cent. silica and 2 per cent. lime;

Jan 1, 1920

COAL is perennially -a subject of major interest at. Pittsburgh, but during the week of Nov. 19 to 24 it was especially to the fore because nearly two thousand persons gathered to take part in the second of the international conferences organized by President Baker of the Carnegie Institute. From the opening session on Monday morning when those attending were welcomed by President Baker and T. P. Gaylord, president of the Chamber of Commerce of Pittsburgh, until the party returned from the Clairton coke ovens on Saturday. afternoon, there was something going on all the time, and usually three sessions were in progress at once.

Jan 1, 1928

THE purpose of this chapter is to present a general outline of the basic open-hearth process for the benefit of students, practicing open-hearth operators, and metallurgists who wish to review the subject. The discussion is limited to a description of the sequence and purpose of the operations, illustrated by data and examples. Subsequent chapters deal with more detailed and fundamental studies of the subject. The function of the basic open-hearth furnace is to convert various types of ferrous material into finished steel of given composition and quality. In comparison with other steel-making methods, the basic open-hearth process is one of the most versatile, both from the stand- point of the raw materials that can be used and the types of steel that can be produced. The process can be considered as a sequence involving melting, refining, and deoxidation. In the case of some types of liquid-metal charges the melting stage is not present, but refining and deoxidation in varying degrees are fundamental features of the process. GENERAL DISCUSSION OF THE BASIC OPEN-HEARTH PROCESS The first consideration in open-hearth practice is the type of charge on which the operation is based. This consists of three components-fluxing, oxidizing, and metallic materials. Fluxes. In the basic process the fluxing material is primarily lime, added in the form of either limestone (CaC03) or burnt lime (CaO). This is supplemented by magnesia (MgO) and lime from the furnace bottom and banks. The function of these fluxes is to form a slag with the silica (SO2), manganese oxide (MnO), iron oxides (FeO and Fe203), and phosphorus oxide (P205) that are produced by the oxidation of varying amounts of the silicon, manganese, iron, and phosphorus in the charge during melting and refining. The slag, composed of the basic fluxes and the neutral and acid oxides, floats on top of the steel bath when the charge is melted. The composition of this slag depends on the amount of each slag-forming element present in the charge and on the extent of oxidation of these elements during the course of the

Jan 1, 1944

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&apos; 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&apos;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&apos; 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&apos; 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