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By Y. L. Yao

It is suggested that the binary alloy systems of transition metals may be classified into groups according to "excess energy"E. For systems with positive ?E, the Laves phase, the TiNi3-, the TiCu3- and the Cudu-type rich in the smaller atom and the TizNi-type rich in the larger atom may exist. For systems with negative ?E and composed of two components of different crystal structures, the X, the Cr3O and the phase may exist on the side of the phase digrattz rich in the component with the higher "solubility factor" value am! the Cudu-type and the disordered hcp phase on the other side; if the crystal structure of two components is the same, the Cudu-type may exist on both sides. For systems with weakly positive ?E and cotnposed of different crystal structures, the u phase and the MgCd3-type may replace the Laves phase and the other types; the X, the Cr3O and the a phase may also exist. Finally, the equirnolar compounds of the CuAu- and the CsC1-type may exist irrespective of the sign of ?E. THERE are many factors which play a major role in the formation of binary intermediate phases in alloys, such as the crystal structure, the electronic structure, the atomic size and the electrochemical factor. To find the simultaneous effects of all these factors on the formation of intermediate phases of every metal would be a difficult task, especially because only a small fraction of experimental facts necessary for the complete formulation is known at present. Thus the past surveys of intermediate phases have been usually confined to few metals, several types of intermediate phases and some but not all controlling factors. In a previous paper1 the idea of "solubility factor" of metals was introduced. Although the suggested values are tentative and empirical, the formation of a continuous series of solid solutions in metals could be correlated with the interplay among the atomic size factor, the solubility factor and the crystal structure factor. The purpose of this paper is to demonstrate qualitatively the interplay of these factors in the formation of binary intermediate phases among transition metals. FACTORS CONSIDERED The Crystal Structure Factor. With rare earths excluded, the transition metals are classified into three common crystal structures listed in Table I. There is arbitrariness in the present classification of several allotropic elements. However, out of seventy-odd continuous solid solutions formed among transition metals, only six of them, namely, those

Jan 1, 1962

By W. A. White

UNDERCLAY squeeze is the plastic flowing of underclay below coal pillars into mined-out entries and rooms. Squeezes may be caused either by wet mine conditions where the moisture is taken up by the clay—making it more plastic—or by the presence of certain clay minerals, such as mont-morillonite, which are plastic when there is enough natural moisture. Under either condition, sufficient stress will cause the underclay to flow. Squeezes may fill an entry or room within several hours, or it may be several months before movement stops. Squeeze areas commonly cover hundreds or thousands of square yards. The Coal Div. of the Illinois State Geological Survey has collected samples of underclays from various mines and from cores drilled by coal companies in the state. From these samples natural moisture content, particle size and particle size distribution, and clay mineralogy are determined. Data from samples collected from the underclay below Herrin (No. 6) coal in the Lumaghi Coal Co. mine near Collinsville, Ill., are used in this report to clarify points in the discussion. Data from samples taken from other mines lead to the same conclusions. A generalized geological section for the area is given in Table I. The underclay below coal No. 6 ranges from a few inches to 3 or 4 ft thick. The upper 6 to 18 in. are noncalcareous; the lower part becomes more calcareous with depth. Limestone nodules become larger with depth, almost grading into the limestone below. In areas where the clay is nearly absent the limestone may thicken to take its place; thus they may complement each other in thickness. There are two types of squeeze areas in a mine. In one type up to 3 or 4 ft of underclay lie in what appears to be a depression in the limestone underneath. This is suggested by a rim surrounding the squeeze area where the underclay is thin and the limestone lies within a few inches of the coal. In the second type the underclay of the squeeze area is surrounded by underclay of similar thicknesses which does not squeeze. Test Methods: Natural moisture content, particle size and particle size distribution, and clay mineralogy were determined by the following methods: Natural moisture is the moisture content a clay contains in its natural environment, expressed in percentage of the weight of ovendried clay (110°C or 230°F). To obtain the natural moisture content, given in Table 11, the clay samples were sealed in containers as soon as the samples were taken in the mines. Particle size and particle size distribution were determined by the pipette method,' and the data were plotted as cumulative curves, Fig. 1, on semi-logarithmic paper. Particle size was plotted on the logarithmic scale and percentage on the arithmetic scale. The quartiles (diameters that correspond to frequencies of 25 and 75 pct) and medians (diameters that correspond to the frequency of 50 pct) of the samples were determined from these curves. The clay minerals were identified from the data obtained by differential thermal' and X-ray powder" techniques. The differential thermal analyses were made on the whole samples, whereas the X-ray analyses were made on fractions of less than 2p. Data and Discussion Moisture Content: After the sealed jars had stood for 24 hr, those that contained squeeze samples had perspired, so that droplets of water had accumulated on the insides of the jars. Table II shows the moisture in the clay after it had perspired for 24 hr. (This perspiring was not noted in samples from nonsqueeze areas.) After perspiration one of the squeeze samples still had a higher moisture content than the samples that did not squeeze. Clay Mineralogy: The thermal analysis, Figs. 2 and 3, indicates that the clay minerals are chiefly micaceous in type; the low-temperature endothermal

Jan 1, 1957

By PAUL AUDIBERT

THE downward trend of metal prices seems to act something like a reagent that precipitates selfishness in most business men's hearts; in the same way the upward trend precipitates altruism. Operators do not say: "I continue working my mine without curtailment because I can afford the present prices while my neighbor cannot and thus will give me way." They say: "I continue working my mine because 1 consider it a service for consumers. They will get better prices on a free market. Any curtail¬ment would be an attempt to raise prices artificially, that is to say, bad economics." Copper producers have learned how fallacious is such an opinion. It perhaps was not fallacious in olden times when all mines were worked on a small scale even if operating on a big deposit. At that time the supply and demand law played fair. When prices were too low and profits were vanishing for many mines, they would. shut at once, then little by little the metal scarcity would induce prices to climb up again; finally these prices would reach the point when it became profitable to again work the closed mines. Re-opening and shutting down mines was then a normal custom. Workers and operators weakly deplored this unstability, but there was nothing effective they could, do about it.

Jan 1, 1931

By M. F. Fogler

An attempt to duplicate Rawdon and Mutchler's experiments showing a reversal of hardness with continued rolling gave negative results, indicating that the phenomenon is not general but depends, probably, on local conditions of rolling. IN A recent paper, Rawdon and Mutchler1 gave some exceptionally interesting results on the Brinell and scratch hardness of severely cold-worked metals. In their work, they found that, on continued cold rolling, the metal hardened up to a particular point and then reversed and became softer; this was true for both Brinell and scratch hardness values. The generally reported behavior2 of metals, with respect to Brinell tests on cold-worked material, is that the metals harden up to a certain point and then, on further cold rolling, no change in Brinell hardness occurs. Jeffries and Archer3 state that there is little difference between the scratch hardness of annealed and cold-worked metals; the work of Faust and Tammann4 also indicated no difference between-the hardness of annealed and cold-worked copper. Rawdon and Mutchler found, when they plotted the reduction ratio (initial thickness divided by thickness after rolling) against the hardness value for the cold-rolled material, that the hardness number increased up to a reduction ratio of about 3 and then decreased and became even smaller than that for the annealed metal. This behavior was reported for both scratch and Brinell hardness; Figs. 1 and 2 show their results for Brinell hardness on the metals for which they published data. This is an exceptionally interesting phenomenon, if it occurs under all conditions of rolling, and would have an important bearing on the practice of cold

Jan 1, 1925

By H. L. Overton, J. B. Lipson

The concept of sodium single-ion equivalent activity as developed by Gondouin, Tixier and Simard,' was used to determine the filtrate resistivity-activity relationships for 150 laboratory and 49 field drilling muds. With the exception of the native and phosphate high-resistivity muds and the calcium-treated muds, the filtrate resistivity-activity relationships were found to be within 20 per cent of that for pure sodium-chloride solutions. Gondouin, et al,* previously suggested a method of treating the high-resistivity muds in quantitative electrical log analysis. A new treatment is presented which uses the P-alkalinity of the filtrate as a correlating parameter in handling the calcium-treated muds in quantitative electrical log analysis. INTRODUCTION Gondouin, Tixier, and Simard in 1957 introduced new interpretive procedures for analyzing the self-potential curve of electric logging. They re-emphasized the previous work of the Schlumberger brothers, Wyllie and others, and re-defined the activity concept in terms of a number which they termed the effective resistivity. Their procedures are particuarly effective when the connate-water resistivities are less than 0.08 ohm-m or greater than 0.3 ohm-m. For gyp muds where the calcium content is known, a procedure was presented which allows calculation of the connate-water resistivity with improved accuracy. These procedures assume that one of the fluids in the system is a pure sodium-chloride solution, but they are not limited by the assumptions. For the fresh and saline connate waters, for instance, it is assumed that the drilling mud filtrate is a pure sodium-chloride solution. For the gyp mud interpretive procedure, it is assumed that the connate water is a pure sodium-chloride solution. Brown,' on the other hand, has suggested that it would be extremely fortuitous if drilling mud filtrates could all be treated electrochemically as sodium-chloride solutions, and he cites some examples where discrepancies exist. A study has been made of the deviations of sodium single-ion equivalent activities, an of drilling mud filtrates from that of pure sodium-chloride solutions. Drilling fluids in common use on the Texas and Louisiana Gulf Coast and laboratory-controlled muds were investigated. Using a cell patterned after Gondouin, et al, (Fig. I), the equivalent activities were measured. It should be remembered here that the activity measured is merely an index which uses numbers that represent the sodium single-ion equivalent activity a,., of the mud filtrate. The membrane potential developed across the cell was determined with a null-type potentiometer. The resistivities of the solutions were measured by the four-electrode method. The resistivity system was calibrated by using saturated KC1 solution as a standard. Chemical properties of the drilling fluids studied were measured with standard API-approved equipment for the particular property in question. For the activity measurements, two shale discs were chosen to serve as cationic membranes. These two discs were both 1 1/4 in. in diameter and, respectively, 1/4 and 1/8 in. in thickness. The membrane potential, Em, was determined using the shale discs as cationic selective membranes separating two standard sodium-chloride solutions of known mean activity. Then by comparing the constant Km in the following equation, with the theoretical value of — 59 mv at 75OF, the perfection of the membrane was determined. The variation of Km for the two membranes used in this experimental work, as well as one of the many unsuitable membranes, is shown in Fig. 2. The measurement of the activity of mud filtrate involves the balancing of its combined individual activities against a standard solution of known mean activity. At the point where there exists zero potential across the membrane cell, the activity effects may be assumed equal for all practical purposes. The mechanics of making a null reading of this sort requires having a large number of different mean activity solutions. A more practical method involves

By H. B. Goodrich

In considering historically oil development in Oklahoma, it must be recognized that basic evolutionary factors interlock and have an effect in common throughout the whole oil industry, regardless of locality or minor problems. Oklahoma, as the third in rank of oil-producing states (Texas being first and California second in production for 1929) has, like the rest, advanced to at least a partial recognition of the words, "Conservation," "Unitization," "Curtailment," "Prora-tion," and especially "Cooperation." Whether through altruism (of which there have been examples) or by exercise of good business common sense, Oklahoma operators realize that the oil business can run itself by cooperative action for the good of all. In this long-continued period of overproduction, Oklahoma has brought the advancing output down to limit of market requirements at least temporarily. Sources of Statistical Data For this paper, figures published by four recognized authorities were consulted. Between themselves these vary only a negligible per cent, in their totals. To be consistent, and on account of earlier availability the estimates published by the Oil and Gas Journal are mainly used herein, supplemented from other public and private sources. General Oil ProdCction in Oklahoma In 1927 Oklahoma's peak of all years was 276,022,024 barrels. In 1928 Oklahoma's total production was 247,500,851 barrels. In 1929 Oklahoma's total production was 252,229,474 barrels. The efforts of proration and curtailment programs on flush and semi-flush districts such as Greater Seminole, Oklahoma City, Logan County and others, with the natural decline of older pools, kept 1929 below 1927, but still the total was greater than in 1928. The total United States production for 1929 is herein taken as estiiated at 1,004,266,723 bbl.† Oklahoma produced 25.1 per cent. Of

Jan 1, 1930

By B. F. Zwick

No new fields have been discovered in Ecuador during 1945, though Shell. Company of Ecuador's Vuano No. 1, near Arajuno in the Oriente concession, which was reported to have drilled to .5281 ft., tested a small, noncommercial quantity of 13° gravity oil. In the upper section, the well tested large flows of fresh water and has been abandoned. Shell is preparing to move to another location.

Jan 1, 1946

By O. J. C. Runnalls, L. M. Pidgeon

J. M. Blocher, Jr. and I. E. Campbell (Battelle Memorial Institute, Columbus, Ohio)—Since the de Boer-Van Arkel process for making titanium metal involves a number of steps in a fairly compact unit, it is difficult to determine simply which of the steps is rate controlling. In any statement as to which step constitutes the rate-controlling process, qualifications appear to be in order. It is possible to design a reaction bulb in which any one of a number of steps is made to be controlling. I—With the filament removed some distance from the crude, as in the case of the authors' experiments, the interdiffusion of iodine and iodide may be controlling. 2—If, as is usually done, the crude metal is placed in a perforated cylindrical basket, or as a briquetted mass, in close proximity to the filament, the rate of deposition is increased (we obtained rates of deposition 5 to 10 times those cited in the authors' paper), and another rate-limiting factor, such as the reactivity of the crude, may take over. In this regard, we have noticed radically different rates of deposition with different crudes, and with crudes in various stages of exhaustion. 3—With a very reactive crude metal and with optimum practical geometry, still another process may be controlling. It is felt that this is a diffusion process in the immediate vicinity of the filament involving the fundamentally adverse situation of a net flow of particles away from the filament. The separate experiments on the reactivity of iodine with titanium are interesting but somewhat inconclusive. Data is still needed on the partial pressure of iodine in an operating decomposition bulb. A knowledge of the gradient of iodine partial pressure from the crude to the filament would be particularly enlightening. Optical absorption may be a useful technique here. Accurate measurements of the total pressure within a decomposition bulb under various conditions would be quite revealing. Preliminary measurements have been made at Battelle in following this line of attack. It is interesting to note that the authors' data on the temperature dependence of deposition rate indicate that the overall rate is not controlled by the kinetics of the decomposition reaction at the filament: TiI1 ? Ti + 4I Any reasonable estimate of the activation energy of this reaction would, if its kinetics were controlling, dictate a much greater temperature dependence than is observed here. The authors apparently attribute the drop in deposition rate (eventually to zero) with increased TiI4 pressure solely to a decrease in diffusion rate. However, there is an equilibrium factor involved here that must not be overlooked. As the partial pressure of TiI4 is increased, a point is reached where, due to the competing reaction of the tetraiodide with titanium to form lower iodides, the equilibrium partial pressure of titanium is reduced to the point that it equals the vapor pressure of titanium at the filament temperature and the deposition rate falls to zero. This effect would

Jan 1, 1953

By William B. Plank

ENGINEERING educators and industries are worried about the engineering manpower shortage that is predicted as a result of the increasing demand for trained engineers not only by industry but by the armed services. This is in the face of a decreasing supply, as is shown by this and other studies. Not only has the number of entering freshmen been decreasing since 1947, because of a decrease in the number of high school graduates entering engineering, but the total number of high school graduates will continue to decrease until 1958 because of the lowered birth rate during the depression years.

Jan 8, 1951

By ANDREW CARNEGIE

Although the noble building provided in New York City by Mr. Carnegie for the United Engineering Society has been pushed to about half-completion, the ceremony of laying its corner-stone was not performed until Tuesday afternoon, May 8, 1906. The stone lies just back of the southeast corner of the building, on the north side-of West 39th Street. Among those present were Mr. and Mrs. Carnegie, Miss Whitfield, the sister of Mrs. Carnegie, Ralph W. Pope, Secretary of the Institute of Electrical Engineers, Frederick R. Hutton, Secretary of the. Society of Mechanical Engineers, Rossiter W. Raymond, Secretary of the Institute of Mining Engineers, Charles H. Haswell, the first Chief Engineer of the United States Navy (1836-1851), now in his ninety-seventh year, John Fritz, of the Bethlehem Steel Company, William H. Fletcher, President of the Engineers' Club, E. E. Olcott, President of United Engineering Society, and other interested friends. After an inspection of the interior of the building, the group formed about the corner-stone, which had been draped with the American flag. The exercises were opened by Mr. Olcott, who appropriately welcomed Mr. Carnegie, and briefly expressed the essential value of the building, saying, in part " The societies to be housed underneath this roof have as their aim the pre¬serving and putting in tangible form of the records of scientific accomplishments so as to avoid the repetition of mistakes. The possibility of finding the records of these results all at one center, so near the great Public Library of our city, will be an inestimable advantage to all professions. It is an occasion of no ordinary moment, therefore, when we can welcome Mr. Carnegie and have him lay for us the corner-stone of this great building which his liberality has provided." Mr. Carnegie responded in happy vein, thanking the committee for their greeting, and expressing his pleasure. in being able to do what he had done to further so worthy a cause. Among other things, he said

May 1, 1906

By H. S. Price, R. L. Reed, J. E. Warren

The behavior of the reverse-combustion process in a linear adiabatic system is theoretically investigated by means of an idealized physical model. T his model is described by a pair of non-linear equations involving heat and mass transfer which are coupled by a concentration-dependent reaction-rate function of the Ar-rhenius type. The differential equations governing the quasi steady-state temperature and concentration distributions are approximately solved by using either physical or mathematical simplifications. It is shown that the reverse -combustion process can be mechanistically described by simple physical models whose behavior equations can be solved formally. It is further demonstrated that the derived reverse-combustion equations can be solved numerically within the error limits for the experimental data. The theoretically predicted peak temperature-flux-velocity relationship exhibits reasonable agreement with experimental data obtained from Athabasca tar sand. The principal contribution of this work lies in its usefulness as a starting point for developing a more comprehensive theory. A description of the vaporization-coking process must be obtained; then, the theory must be extended to three dimensions to include geometrical effects and heat losses. INTRODUCTION In another paper,'" he physical processes visualized as occurring during reverse combustion have been described. In this paper, the extent to which an elementary theory can account for experimental observations is determined. Theoretical results that can be used to estimate some of the behavior characteristics of importance to this process are also presented. Since it is not possible to include all the features of the combustion mechanism of which we are currently aware, the mathematical formulation refers to the highly idealized system developed herein. This simplified physical model is based on the simultaneous transfer of mass and heat accompanied by a chemical reaction: it is described mathematically by a pair of coupled, nonlinear differential equations. Similar sets of equations have been studied extensively in the field of flame propagation; an excellent review of these investigations has been published by Evans.1 FORMULATION OF THE PROBLEM It will be recalled that the experiments are performed with a thin-walled cylindrical tube that is uniformly packed with sand and oil. The system is maintained substantially adiabatic by means of heat supplied externally in such a way that the radial temperature gradient in any plane normal to the axis of the tube approaches zero. Initially, the tube is at ambient temperature, except at one end where it is rapidly heated to a predetermined temperature. When the prescribed temperature is achieved, air is caused to flow into the cold end of the tube. As the oxygen in the air stream contacts the hot oil, a localized exothermic reaction takes place. The generated heat is conducted and convected away from the reaction zone so that definite temperature and concentration profiles are rapidly established and move uniformly in a direction opposite to that of the air flow (Fig. 1). As a consequence of this mode of oxidation, all of the oxygen in the air is consumed; then, the remaining nitrogen and the gaseous combustion products sweep out all vaporized hydrocarbons and leave an immobile hydrocarbon-coke on the sand.

By Charles B. Dudley

While working, during the summer of 1877, upon the "Chemical composition and Physical Properties of Steel Rails," the results of which are given in my report with this title, I was struck with the surprising wear which some of the rails, which would ordinarily be called soft rails, had endured. At that time I knew of no chemical measure of softness except low carbon, and I found that a numher of rails with low carbon had endured as high or higher tonnage, with apparently as little loss of metal by wear, as those with higher carbon. My own work on steel rails that summer did not embrace any definite experiments as to the amount of metal worn off the rail per million tons which had passed aver it; and so I could get no more definite answer from that work, to the question at the head of this paper, than was given by comparing the appearance of the worn section of the rail with its tonnage. This comparison, however, served to arouse in my mind the query, whether the commonly received opinion as to the relation between the hardness and wearing power of steel is correct, as applied to steel rails. This opinion, if I am right, is: the harder the steel, the better will be the wear, and the limit of hardness is simply one of safety; hard, brittle steel being, of course, more liable to break than soft, tough steel. The query, although aroused, did not bear any immediate fruit, and, as will be evident to any one reading it, the report above referred to was written with the commonly received opinion in mind. Since that time I hare collected a little information upon this subject, which I should be glad to submit to the Institute, if for no other purpose, for the sake of arousing attention, and directing study to the question of hardness versus wear in steel rails. Before making known this information, howevcr, permit me a few words in reference to hardness. How shall we measure the hardness of steel ? Of the various ways of getting indications as to the hardness of steel, which are known, three mill serve our present purpose. These are: 1st. High carbon. It is generally agreed, I think, that at least within proper limits, the greater the amount of combined carbon in a piece of steel, the harder the steel, and I need not do

Jan 1, 1879

By Chas. B. Dudley

WHILE working, during the summer of 1877, upon the "Chemical Composition and Physical Properties of Steel Rails," the results of which are given in my report with this title, I was struck with the surprising wear which some of the rails, which would ordinarily be called soft rails, had endured. At that time I knew of no chemical measure of softness except low carbon, and I found that a number of rails with low carbon had endured as high or higher tonnage, with apparently as little loss of metal by wear, as those with higher carbon. My own work on steel rails that summer did not embrace any definite experiments as to the amount of metal worn off the rail per million tons which had passed over it; and so I could get no more definite answer from that work, to the question at the head of this paper, than was given by comparing the appearance of the worn section of the rail with its tonnage. This comparison, however, served to arouse in my mind the query, whether the commonly received opinion as to the relation between the hardness and wearing power of steel is correct, as applied to steel rails. This opinion, if I am right, is: the harder the steel, the better will be the wear, and the limit of hardness is simply one of safety ; hard, brittle steel being, of course, more liable to break than soft, tough steel. The query, although aroused, did not bear any immediate fruit, and, as will be evident to any one reading it, the report above referred to was written with the commonly received opinion in mind. Since that time I have collected a little information upon this subject, which I should be glad to submit to the Institute, if for no other purpose, for the sake of arousing attention, and directing study to the question of hardness versus wear in steel rails. Before making known this information, however, permit me a few words in reference to hardness. How shall we measure the hardness of steel ? Of the various ways of getting indications as to the hardness of steel, which are known, three will serve our present purpose. These are: 1st. High carbon. It is generally agreed, I think, that at least within proper limits, the greater the amount of combined carbon in a piece of steel, the harder the steel, and I need not do

Jan 1, 1879

By S. R. Zimmerley, S. F. Ravitz

High-grade cobalt concentrates were produced from the complex Blackbird ore with very good recovery in continuous pilot-plant operations in which a low-grade bulk cobaltite-pyrite flotation concentrate was roasted in a multiple-hearth furnace to oxidize the pyrite selectively. The cobaltite was floated from the resulting calcine.

Jan 1, 1950

Jan 1, 1912

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of gas-solid reactions with special attention given to the hydrogen reduction oj dense spheres of hematite. This reduction process must pvoceed through a sequence of transport and chemical .reaction steps acting in series. Under typical experimental conditions, none oj the individual transport and reaction resistances may be neglected in the development of a physically significant model. A linear vate of thickening oj the product layer, usually taken as evidence of interface-controlled .reuction, may be observed even though transport resistances play a dominant role in the over-all kinetics. The temperature and pressure dependencies of all terms have been carefully evaluated in order to .make fill use oj arailable expe-inzental data in evaluation oj the model. FOR obvious technological reasons, the kinetics of reduction of iron oxides has become the subject of intensive experimental and theoretical investigation during recent years. Continuing efforts to construct mathematical models to describe the kinetics of reaction between a gas stream and a granular bed of solid particles have demonstrated the necessity of a thorough understanding of the reaction kinetics of a single particle within the system as a prerequisite to the construction of physically significant models of complex, reacting systems. This paper presents a critical examination of the transport and chemical-reaction processes involved in single-particle oxide reduction and develops the mathematical expressions necessary to evaluate their importance. Comparison of theoretical predictions with experimental results contributes important new understanding of the complex nature of this process. The reduction process has been studied under a wide range of experimental variables, and it is not surprising that apparent conflicts in observation and interpretation appear in the literature. The interested reader is referred to the reviews of Themelis and auvin"? and Manning and philbrook3 for a description of much of this work. The course of reaction commonly has been followed by measuring the oxygen weight loss from the particle as a function of time. A number of authors have suc- cessfully correlated their data in terms of a model which assumes that the reduction process is controlled by the rate of reaction at a single, sharply defined, advancing interface. According to this model, the interface will advance linearly with time. A mathematical model for gaseous reduction in a packed bed developed by the present authors in an earlier paper4 recognized that reduction must proceed through the series hematite (Fe203), magnetite (Fe30,), wiistite (Fe,O), and finally metallic iron. The reduction scheme permitted a stepwise topochemical reduction of the individual particles to metal or to the lowest oxide thermodynamically possible for the local gas composition in the bed. The limiting situations of theoretically dense and very porous oxide structures were considered. On the basis of available experimental evidence, the simplifying assumption was made in each case that all product layers would thicken linearly with time. A generalized single-particle model has now been developed to determine the significance of transport resistances in the product layers and in the gas film surrounding the particle. The analysis shows that the interplay of transport and chemical resistances is such that an apparently linearly advancing interface may be observed despite the fact that the reaction may be under significant transport control. Attention thus far has been focused on the development of a model for the topochemical behavior of dense spheres of hematite in atmospheres capable of reducing them completely to metal. The formation of successive product layers of iron, Fe,O, and Fe304 is assumed to follow the mechanism originally described by dstrijm.' All oxygen removal from the core occurs at the iron/Fe,O interface, intermediate oxide layers being propagated by sol id-state diffusion without change in the oxygen density of the core. Since fractional reduction is operationally defined in terms of oxygen weight loss, the kinetics of the over-all reduction of FeZ03 to iron is properly studied in terms of the gas-solid reaction occurring at the iron-wiistite interface. The fractional reduction of a partially reduced oxide sphere is given by: here refers to the radial position of the iron/Fe,O interface. This model is not universally applicable because, as explained in the earlier paper,4 a consideration of porous particles or of dense particles in atmospheres not capable of reducing wiistite must allow for the possibility of gaseous reduction at interfaces other than the one between iron and Fe,O. However, evidence that certain hematite specimens actually do follow the dense-pellet mechanism developed here is provided by the data of cewan' and of Bogdandy and

Jan 1, 1967

By S. S. Cole, H. Sigurdson

The melting points of mixtures of titanium dioxide and other titanates have been reported to a limited extent as binary systems and some results have been reported in conjunction with silicon dioxide. The limited data indicated that a low melting zone might exist in a ternary or quarternary system of CaO-MgO-TiO2-Al2O3, since the eutectics reported in the binary systems of MgO.TiO2-TiO2, Al2O3TiO2-TiO2 and CaO.TiO2-TiO2 were of about equivalent composition of TiO2. The importance of a low melting region with a high titanium oxide value in the developing of high titanium slags is fully appreciated by metallurgists. A comprehensive study was undertaken to establish basic information on low melting titanate mixtures. Compounds in the System CaO-MgO-TiO2 -Al2O3 Preparation of the titanates of CaO, MgO and Al2O3 confirmed reported data that the following compounds could be formed under oxidizing conditions in solid state reactions: CaO.TiO2, 2MgO.TiO2, MgO.TiO2, MgO-2TiO2 and Al2O3.TiO2. Under oxidizing conditions it was not possible to react MgO with TiO2 in mol ratios higher than 1:2 without having unreacted TiO2 in the product, nor was it possible to form calcium or aluminum titanates with a higher mol ratio of CaO and A12O3 to TiO2 than 1:1. By fusing mixtures of Al2O3-TiO2 and MgO-2TiO2 together a series of solid solution products were obtained, which showed an MgO-2TiO2 X ray diffraction pattern shifted to smaller inter-planar spacings. Range of Investigation Data in the literature1 indicated that these titanates had melting points which ranged from 1645 to 1860°C. Since the purpose of the study was primarily to provide useful data for smelting titaniferous ores, the work was restricted to the zone of the system which would include the crystalline phases present in the slags. The explored limits were bounded by CaO.-TiO2-MgO.TiO2-TiO2in the base plane. The system was extended to a fourth component Al2O3-TiO2 since many titaniferous ores contain appreciable amounts of A12O3. In the quarternary system CaO-TiO2-MgOTiO2-TiO2-Al2O3TiO2, a tetrahedron was used to represent graphically the components, with one component at each point of the tetrahedron. In the base plane, mixtures were pre- pared to represent fairly uniform changes of composition over the desired range expressed on a mol percent basis. Al2O3-TiO2 was brought into the system in increments of 10 mol pct up to 40 pct. Mixtures were then made up for each of the Al2O3-TiO2 planes. The ranges employed were then represented by five planes cutting the tetrahedron at 10 mol pct Al2O3-TiO2 intervals. Choice of Equipment Although it was necessary for all smelting work to be done in a strongly reducing atmosphere, it was decided that all melting point determinations should be done under oxidizing conditions. This decision was prompted by the fact that TiO2 reduced to lower oxides in a reducing atmosphere with consequent changes in melting points. The use of a micropyrometer and a platinum strip furnace for work of this type is adequately described in the literature.2 With modifications, equipment was selected which provided a fairly rapid method of determining melting points of refractory oxides. The final assembly, which was used, consisted of a platinum strip furnace and a Leeds and Northrup disappearing filament optical pyrometer attached to a special telescope which magnified the sample about 20 diam. The furnace assembly consisted of a platinum strip 0.005 X 0.3 X 2.2 in. mounted on brass posts on a refractory base. This was enclosed in a black steel shell which had a 2-in. opening at the top for purposes of sighting the telescope. The platinum strip was in series with two 0.04 ohm nichrome resistors connected to the secondary of a 2 kw transformer which supplied 17 volts. The current to the primary was varied

Jan 1, 1950

By G. E. McElroy

MUCH attention has been directed to mine-air flow in recent years, more especially in Great Britian where there is frequent reference to a theory of fluid flow developed by English engineers. Briefly stated, this theory is that for similar passages of the same relative roughness, in which fluid flow occurs, the conditions of flow are exactly the same for equal values of the product W D V/ µ, where W = density of the fluid, D = diameter of the passage through which flow occurs, V = mean velocity of flow, and µ = absolute viscosity of the fluid flowing. This, the "Reynolds Criterion" of fluid flow, had its origin in the work of Prof. Osborne Reynolds' more than 40 years ago. Later, Lord Rayleigh amplified the theory2 which has been conclusively proved for small pipes by the experiments of Stanton and Pannel3 over a large flow range, and by Lacey4 over a somewhat more limited range. Concordant results on small pipes have also been obtained by numerous other investigators with single fluids over more or less limited ranges of flow. According to this theory results in one medium, such as water, are immediately applicable to another, such as air; and experimental results on models are (theoretically, at least) applicable to full-scale designs. This is of great importance in aeronautics and can be of considerable value in mine ventilation research. Hodgson, in a recent paper,5 has outlined the application of this theory to mine-air flow and recent English experiments" on the resistance of a timbered mine airway have been expressed in this form.

Jan 10, 1926

By J. W. Downey, M. V. Nevitt

MUELLER and Knott' have reported that Ti2Cu has the Si2Mo-type (Cllb) structure. The lattice parameters of Ti2Cu and the positions of the titanium and copper atoms are given by them as follows: ao = 2.944A; co = 10.786A 6 atoms per unit cell: 2 Cu (a) 000; 1/2: 1/2, 1/2 4 Ti (e) 002; 1/2, 1/2, 1/2 + z 00 -2 ; 1/2. 1/2. 1/2- z where z = 0.341 We have found eight other binary compounds which appear to be isostructural with Ti2Cu. All of them involve the combination of a titanium group element with a copper group element or a titanium group element with palladium. The compounds and their lattice parameters are given in Table I. The alloy samples were prepared by arc melting metals having a purity of 99.9 pct or better. They were homogenized for 72 hr at 900°C in evacuated capsules and quenched in tap water. Filings were prepared, and these were reannealed for 4 hr at 700°C, also in evacuated tubes. The lattice parameters were determined by a least squares Bnalysis of the back reflection lines of patterns made with cobalt radiation. It was not possible to make a precise determination of the lattice parameters of Zr2Au because the filings underwent rapid oxidation at room temperature. The evidence supporting the large tetragonal cell containing 6 atoms involves the presence of the reflections 002, 101, 004, 112, 114, 202, and other reflections with higher indices for which I = 3n. Three or more reflections corresponding to these indices, which cannot be indexed on the basis of a small body-centered tetragonal cell containing 2 atoms, are observed in the patterns of all of the compounds listed in Table I. They are strongest and most numerous when the components have large differences in their atomic scattering factors, as is the case in Ti2Pd, Zr2Cu, and Hf2Cu. The values of the z parameter should be regarded as approximate They were selected on the basis of the best agreement between the observed intensities of two pairs of closely spaced powder pattern lines (004): (112) and (114): (202) and the corresponding intensities calculated for several values of z. An ordering scheme was assumed in which titanium, zirconium, or hafnium atoms occupy the titanium positions of Ti2Cu, and copper, silver, palladium, or gold atoms occupy the copper positions. Calculated and observed intensities of the aforementioned lines and the other lines of the patterns are in satisfactory agreement, but a refinement of the z parameters and a final confirmation of the ordering arrangement must await a more detailed study. It is interesting to note that in transition metal systems at A2B stoichiometry the Si2Mo-type structure competes for stability with two other fre-

Jan 1, 1962

W. 0. HOTCHKISS,* Madison, Wis.-When we began to do geological field work in the Lake Superior region, we found a correlation in existence, and, as youngsters, accepted all that as settled. Both Mr. Allen and I, since that time, have seen a great many things that were not apparent nor visible to Van Hise, and those who worked with him; we realize now that the correlation was not final and that much remains to be determined concerning geology of the Lake Superior region. My attitude on this matter is that we should not publish an amended correlation as a final thing. We should avoid, in every way possible, foreclosing the minds of those who follow us in working in the geology of this region. As a matter of fact, no correlation can be final at present, because facts and data are accumulating so rapidly that every classification must be immediately modified to fit further observation. Consequently, my attitude in this matter would be, instead of saying that the iron formations of the Lake Superior region are all Middle Huronian, to say that there may be three Huronians-or four or five- we do not know. I believe it is better policy to hold to our present correlation. I do not believe there is any economic benefit to the mining man or the geologist working on problems relating to explorations for iron ore, that cannot be just as well solved by maintaining our present correlation, with a. wholesome idea of our lack of knowledge and the necessity for further detailed work. Then, if any new horizons are discovered in any particular range, the minds of the investigators will not be foreclosed because some one has said that all the iron formation is in the Middle so that there is no use looking elsewhere for it. There is use looking elsewhere, in many cases, as the ore deposits become exhausted.

Jan 1, 1920