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By John D. Ridge, Betty S. Moriwaki

One of the most profound economic forces operating on a global scale is the movement of metals, ores, and concentrates from one country to another. A single shipment can pass through a series of ports and leave a flow map looking like some psychological nightmare. Statistical tracing often proves as difficult. How much did one given country send to another? Does the word ton represent the same thing to all people? What part did free ports and transshipment play? Where did the metal finally stop traveling and enter fabrication? The amount of mineral produced in the form of concentrate and as refined metal can be tracked down in the Minerals Yearbook of the U. S. Bureau of Mines. Quantities imported by the U. S. can also be found in that publication. But the Yearbook will not tell what happened to the metals that did not find its way to the U. S. Even after a study of supplementary literature, such as the USBM Mineral Trade Notes and the publications of the International Tin Study Group and of other private and public organizations, the picture remains vague at best.

Jan 5, 1955

By E. J. Rapperport, J. P. Pemsler

The thermodynamic activities of zinc in six solid solution Cu-Zn alloys ranging from 5 to 35 at. pct Zn were determined experimentally in the temperature range 400° to 600°C. This low temperature investigation was canducted in order to evaluate techniques developed to utilize the inherently high sensitivity of atomic absorption flocesses in the measurement of thermodynamic activities. Analytical expressions ,for the activity and actizlity coeflcient are given for the six alloys in the temperature ranges investigated. RELATIVELY few experimental methods are available for investigation of thermodynamic activities of alloys, especially in the solid state. The techniques most frequently used have been the electrochemical potential and the effusion methods, both of which have severe limitations in many instances. It is therefore desirable to expand the ability to perform such measurements in order to obtain new information as well as to provide an additional independent verification capability. In this work, we present a significant improvement in the spectrophotometric method for sensing small vapor pressures in static absorption cells. Similar techniques have been used previously;1"5 however, applications had been limited to relatively high pressures, often greater than 1 torr. Prior investigators have, for the most part, used broad spectral sources such as xenon or mercury lamps, and high intensity arcs. Hollow cathode sources were first suggested in 1956 6 and were used soon afterwards.4'5 These sources offer significant improvements in sensitivity and freedom from interfering spectral lines.'-' EXPERIMENTAL High purity zinc was obtained from Cominco Products, Inc., and copper from American Smelting and Refining Co. Both elements were of 99.999 pct purity. Copper-zinc alloys were vacuum melted in a high fired carbon crucible with each alloy pulled from the melt as a 4 -in. diam bar. The bars were swaged to -1/4 in. rods and vacuum annealed for 160 hr at 800° + 1°C. Samples for gross chemical analysis were taken at intervals along the length of the rods to ascertain the axial zinc gradient. Electron microprobe analysis of homogenized specimens indicated that the alloys had uniform compositions over their cross sections on a macro (200 p) and micro (1 u) scale to better than *1 pct (20) of the gross composition. This tolerance was determined by counting statistics, rather than assured composition fluctuations. All SiO 2 windows were high-ultraviolet-transmission grade to minimize intensity losses. Silica absorption cells were scrupulously cleaned consecutively in organic solvents, dilute HF, and distilled water before use. The empty cells were then flamed while under a dynamic vacuum, cooled, and removed to an argon-filled glove bag. Alloy pieces were cut and filed in the glove bag to produce fresh surfaces, and then loaded into the cells. The loaded cells were temporarily sealed, removed from the glove bag, reevacuated to 10-5 torr or better, and permanently sealed. The instrument used is schematically shown in Fig. 1. The spectral emission from a commercially made hollow cathode lamp (A) of a selected element is focused through an absorption cell (B) inside a well-controlled furnace (C). The intensity of the transmitted beam is measured using the spectrometer* (D) 'Techtron model AA4 atomic absorption spectrometer. which contains a grating (E) that disperses the light prior to impingement on the photomultiplier (F). The monochromator grating is adjusted so that only the wavelength of interest is measured. The power supply delivered an interrupted voltage to the lamp, causing a chopped radiation output to be transmitted. The detector read only the intermittent component of radiation incident upon it, so that all continuous noise signals (furnace radiation, and so forth) were eliminated. Three recording thermocouples contained in the muffle furnace were positioned along the length of the absorption cell: one at each end and one at the center. An effort was made to keep the ends of the cell several degrees hotter than the center to avoid window condensate. Appropriate thermal corrections were then necessary to relate cell pressure to radiation attenuation. Water-cooled heat shields, as shown in Fig. 1, were found to aid signal stability by protecting the hollow cathode and the photomultiplier from furnace radiation. The furnace had a 2-in. diam muffle, Kan-thal wound, with SiO 2 windows at its ends to minimize convective effects. The hollow cathode radiation was masked and focused to form a conic beam that was a maximum of { in. diam within the furnace. Thus, the 1.5 in. diam absorption cell easily contained the entire beam. The furnace was mounted on ball-bearing slides with positive positioning detents. This arrangement allowed the removal of the entire furnace assembly from the radiation path, position [I], Fig. 1, so that frequent sampling of the unattenuated beam intensity could be obtained. In all cases the beam intensity was kept constant to 0.1 pct as judged by readings taken immediately before and immediately after data collection. Only data for absorptions of less than 80 pct were utilized, as systematic deviations from linearity were found for greater absorptions.

Jan 1, 1970

By J. W. Spretnak, R. Speiser

IT has been suggested that boron in steel may form a film entirely around the austenite grain and that this film is responsible for the boron hardenability effect. In this connection, it is of interest to examine some of the ramifications of the concentration range of boron usually employed in hardenable steels, namely 0.0005 to 0.003 pct in a grain size range of ASTM grain size No. 1 through No. 10. The ratio of the iron to boron atoms and the number of unit cells of y iron per boron atom are listed in Table I. Even at the highest concentration considered, there are 1600 unit cells of y iron per boron atom, assuming a uniform distribution of boron. To investigate the possibility of the boron film formation, the number of boron atoms required to cover the grain surface completely must be calculated. With some transition elements, boron crystallizes in sheets composed of equilateral hexagons very much like graphite.' The selected value for the length of a side is 1.80Å. A simple calculation shows that two boron atoms cover an area of 8.4x l0 -16 sq cm. Table II lists the number of atoms of boron required for the formation of the monatomic film and Table III lists the number of boron atoms per grain. The hypothetical cases of 100 pct and 10 pct adsorption are calculated (all boron atoms in a grain and 10 pct of all boron atoms in a grain are located at the grain surface respectively). In Table 111, all combinations of grain size and composition below and to the left of the solid line (100 pct adsorption) and the dashed line (10 pct adsorption) are excluded as to the possibility of covering the grain surface with a continuous boron film. Thus, even for 100 pct adsorption, the smaller grains can form the film only at the higher concentrations. For the best case, grain size No. 1 and 0.0030 pct B, the required degree of adsorption is 3.9 pct. The above calculations deal only with the number of boron atoms required to form a monatomic film and do not take into account the mechanism of concentration of boron at the grain surface and the possible limitations to the extent of this concentration at a constant temperature, as for example in the austenitizing process. The question next arises as to how this surface concentration can occur during an isothermal treatment. Such surface enrichment of boron must occur through the phenomenon of surface adsorption, i.e., the concentration of solute atoms in solid solution in the vicinity of the surface without precipitation. A solute atom will tend to concentrate at the grain boundary if it reduces the interfacial tension. The possibility of adsorption effects involving both boron and carbon in iron has been discussed.' In general, the tendency for a sol-

Jan 1, 1954

By R. M. Goldhoff, J. W. Spretnak

IN connection with establishing the mechanism by which boron enhances the hardenability of heat treatable steels, this research work has been undertaken. Spretnak and Speiser1,2 indicated the need for studying high temperature effects in boron steels and, chief among these, the possible nonhomogeneous distribution of boron in iron grains. The occurrence of this effect may be of significance in explaining the mechanism of enhancement of hardenability by boron as well as in explaining some of the observed characteristics of boron steel behavior. Primarily, then, this work was undertaken a) to establish whether or not boron is adsorbed in ? solid solutions, b) to determine the nature of any such adsorption effects, i.e., whether it is positive or negative as well as its temperature coefficient, and c) to establish the magnitude of any such effect. While past literature on this specific subject is rather sparse, a number of authors have postulated that the observed temporary loss of hardenability as well as the occurrence of the characteristic boron constituent in these steels is due to the nonuniform distribution of boron in austenite.3-0 Experimental Techniques Attempts to obtain direct evidence of grain boundary effects in boron steels have been unsuccessful, both by using the technique of Chalmers' in which small concentrations of solute made radioactive by irradiation are detected by autoradiographic means, and by means of studying cleavage fractures with the electron microscope.8 The present study attempts the design of experiments to measure the effect of boron on properties which might be subject to variation because of grain boundary effects. A study of the theoretical aspects of grain growth indicates that such studies may be pertinent. Another valid type of experiment involves the measurement in polycrystalline materials of properties whose values depend on the bulk of the grain, being negligibly influenced by grain boundaries. One such property is the lattice parameter measured by X-ray diffraction. The value of the lattice parameter reflects the average conditions which obtain over a relatively large number of atoms in a fixed crystalline lattice, and is therefore mainly dependent on bulk grain material. Measurement of lattice parameter variation over the austenite range of temperature in iron with and without boron should give evidence of concentration variations in the bulk grain material if adsorption effects are significant. Finally, use is made of the Grange and Garvey3 metallographic test for boron in which a characteristic boron constituent can be developed in austenite grain boundaries. The very occurrence of this phenomenon suggests grain boundary enrichment of boron and a study of the occurrence of this constituent and its varation with austenitizing temperature should help to detect grain boundary effects. Materials One lb ingots of pure iron, an Fe-B alloy, an Fe-C alloy, and an Fe-C-B alloy were prepared. The melting technique included an initial melting of electrolytic iron under vacuum followed by remelting under hydrogen and, finally, by melting under argon with the addition of alloying elements. Each ingot was surface machined between meltings. A quantitative spectrographic analysis was obtained on the pure ingot and, in addition, oxygen, nitrogen, and carbon were determined by the vacuum fusion method. The results of these analyses are given in Table I. Semiquantitative spectrographic analyses were performed on the alloy ingots, while quantitative determinations of the alloy additions were obtained. These analyses are shown in Table 11. The cast ingots were subjected to the following sequence of fabrication treatments: forging to 5/8 in. bars, swaging to 0.300 in. rounds, drawing to 0.025 and 0.010 in. wire. Portions of each ingot were retained in the swaged condition for experimental use. For certain portions of the work typical commercial steels were used. These materials were supplied by the Republic Steel Corp., Canton, Ohio, and correspond to AISI 8640 and AISI 86B40 compositions.

Jan 1, 1958

By N. J. Olson, G. W. Toop

A regular solution is characterized by a finite molar heat of mixing and entropy due only to ideal or random mixing. The thermodynamic properties of binary regular solutions which exhibit constant atomic coordination number and constant atom-atom intefac-

Jan 1, 1967

By W. F. Holbrook

IN a previous paper1 a method for the measurement of the comparative desulphurizing power of slags was described and data were presented covering the range of likely slags containing up to 10 per cent MgO In the present work the range is extended to include slags containing up to 20 per cent MgO, and the effect of temperature on 5 per cent and 15 pen cent MgO slags over the range 1475° to 1525° C is included The method used was that described in the previous paper except that some of the temperature measurements were made with a noble-metal thermocouple instead of a tungsten-graphite thermocouple Twelve-gram charges of 0 8 per cent sulphur-metal and 5-gram charge-, of slag were subjected to heating for 30 nun at a prescribed temperature The charges were analyzed for sulphur content For purposes of comparison, desulphurizing power is defined as the ratio of the percentage of sulphur found in the slag to that found in the metal Six slag and metal charges were made coincidentally in 5/8-in holes in a section of an electrode graphite rod One slag and metal charge was used as a control by means of which adjustment in the desulphurization value could be made for small variations in temperature and other factors For convenient presentation of the data, the slags are arranged in groups in each of which one of the four main slag components is constant Thus, the 15 per cent MgO slags are presented separately from those containing 20 per cent MgO SLAGS WITH MAGNESIUM OXIDE CONSTANT 15 Per cent MgO -The data on slags containing 15 per cent MgO cover a composition range of 24 to 50 per cent SI02, 5 to 27 per cent A1203 and 24 to 53 per cent CaO Variation in composition has been in steps of 2 per cent over much of the area Because the change in desulphurization power is generally gradual with gradual change in composition, certain sections have been covered m steps of 4I per cent and even

Jan 1, 1938

By T. J. Koppenaal, M. E. Fine

A yield point effect attributed to short-range ordevi?g (SRO) occurs in Cu base Al. At at 296°K varies with heat treatment, decreasing as the annealing ternperature is raised .from 433Oto 598°K. Davies aid Cahn' observed a corresponding decrease in SRO. (523 °K anneal, measured at 77°K) is approximateZy proportional to the variations of A7 with strain rate and testing temperature are also Consistent with the idea that is associated with SRO. A preliminary investigation of the tensile properties of a Cu-Al single crystals showed the presence of a rather strong yield-point effect (drop in flow stress after initial yielding). The object of this research was to investigate its origin and behavior. a Cu-Al alloys are particularly interesting because diffuse X-ray scattering measurements by Davies and Cahn,' Houska and Averbach,' and Borie established the presence of short-range order. The degree of local order may be changed with heat treatment.' cottrel14 suggested that the presence of local order might result in a yield-point effect, and thus the possibility exists here for experimentally ascertaining the importance of short-range order with respect to yield points in these alloys. Since a 12 pct difference exists between the atomic sizes, elastic or Cottrell locking5 must also be considered. Further, Howie and swanne have shown that the stacking fault energy of copper is reduced by aluminum additions. The width of extended dislocations should thereby increase. hus the conditions appear attractive for Suzuki locking.' Finally, the possibility of stress-induced order at dislocations, schoeck locking,' must also be examined, EXPERIMENTAL PROCEDURE Alloys up to 14 at. pct Al were prepared by induction melting high-purity (99.999 pct) Cu and (99.996 pct) Al in a graphite boat under a dynamic vacuum of 5 X 10o mm of Hg. After homogenizing the ingots at 900°C for at least 24 hr under vacuum, they were rolled with intermediate anneals to strips 1.55 mm thick. Single crystals 10 in. long were grown by lowering strips, contained in a split graphite mold sealed in fused quartz at 5 X lo-' mm of Hg, through a single coil induction heater at a constant rate of 1/2 in. per hr. Tensile specimens 1.25 in. long were cut from the single crystal strips and reduced cross sections about 0.7 in. long and 3.0 to 3.5 mm2 in area were introduced by filing and abrading.8 To remove the worked portion about 10 pct of the cross-sectional area was removed by etching. Back-reflection Laue photographs of a filed and etched specimen were taken before and after annealing at 900°c for 24 hr. Small, well defined Laue spots were obtained with no visual difference in the two photographs. Further, specimens with and without the reduced sections began yielding at about the same stress. Hence, for our purposes, filing and abrading did not affect the structure of the specimens. Each single crystal specimen was annealed at 900° c in vacuum for at least 24 hr and furnace cooled; while cooling through the range of 250o to 200°c, the rate was about 55°C per hr. Orientations were determined by the usual back-reflection Laue

Jan 1, 1962

By Warnie Flint

PERSONAL INJURY ACCIDENTS According to statistics compiled by the National Safety Council, US Bureau of Mines, American Medical Association, and other agencies, accidental injuries cause more deaths than all the leading diseases. NO one is immune to an accident. Probably the best way to describe an accident is to say that it is an unexpected happening. The automobile driver is not expecting a terrifying crash, the electrician does not expect to be electrocuted, nor is the coal miner expecting the roof to fall on him. All personal injuries will not result in death. There is a multitude of victims who are living proof of what accidents can mean to an individual-victims who are blind, paralytic, missing arms, legs, etc. In most instances the earning power of these individuals is gone, and they are utterly dependent upon family or welfare. For many years there seemed to be an attitude that prevailed in industrial America that accidents were inevitable, and that so many fatalities and injuries should be expected. This, of course, was utter nonsense. Since the birth of such organizations as The National Safety Council, American Society of Safety Engineers, and the US Bureau of Mines, much progress has been made in reducing accidents. The enactment of compensation laws greatly contributed to the progress that has been made. Does this mean that all accidents can be prevented? Unfortunately, it does not. Human psychology indicates that men will work unsafely or perform unsafe acts for the following reasons : 1) Lack of knowledge or skill. 2) Conflicting motivations, such as: (a) to be more comfortable, (b) to save time or effort, (c) to be accepted by a group. 3) Physical or mental condition. Nearly everyone desires his own safety, but not all individuals are willing to do what they know to do to insure their own safety.

Jan 1, 1981

THE translators wish to record their appreciation of the help given by many individuals with whom they have discussed various details of the work. They are particularly indebted to Mrs. Anne Noble McKeachie, who initiated their collaboration; to Miss Cora Adamson, who spent many hours in making an accurate copy of a much-mutilated &st draft of the translation; and to the Yale University Library which gave access to its excellent collection of books on all aspects of the history of the sciences. The reader will share with the translators their obvious indebtedness to Mr. Carl P. Rollins, Mr. James W. Boyden, and the staff of the Printing-Office of the Yale University Press. The publication of this translation by the American Institute of Mining and Metallurgical Engineers has been made possible by a grant from the Seeley W. Mudd Memorial Fund, administered by a committee composed of Harvey S. Mudd, H. DeWitt Smith, and George Otis Smith. The translators are gratified that their work has been judged to fall within the scope of this Fund, which was established for the advancement of the sciences of mining and metallurgy by the encouragement of research and the dissemination of knowledge, and especially for the furtherance of such activities as might benefit the younger members of the profession. While Biringuccio's book would scarcely serve as a dependable text for the young mining student or metallurgist, it can give him a sense of his membership in a long-standing and honorable profession and enable him better to see his own work in true perspective. It is hoped that this English edition of a sixteenth-century Italian work will be read by the practicing metallurgist as well as by those who have already found pleasure in exploring the past of their profession. A man always feels more at home in a foreign country with men of his own craft than in his birthplace with those of different interests: As in space, so in time, and the modem metallurgist who may be unmoved by the literary and artistic Renaissance will quickly appreciate the spirit of that exciting period as he talks shop with Biringuccio on a visit to mine, smelter, forge, and foundry; as he sees in different forms the very furnaces and machines whose operation and response he knows so well; and as he discusses with this engineer of four centuries ago such topics as the best kinds of fuel or refractory for a given operation, and the importance of adequate supplies of power and material.

Jan 1, 1942

By E. L. Dougherty, J. W. Sheldon

A numerical method for computing the dynamical behavior of fluid- fluid interfaces is described. Results of studies made to assess the accuracy and economy of the method on a computer are reported. It is concluded that it is practical to obtain digital computer solutions for fluid- fluid interface problems with two space dimensions. PROBLEM DEFINITION We consider two-dimensional flow in a rectangle as shown in Fig. 1, where a fluid-fluid interface divides the rectangle into two regions. The pressure is specified along the lower boundary (the injection boundary) and upper boundary (the withdrawal boundary). There is to be no flow of fluid across the side boundaries, which are walls of symmetry for the flow, and px = 0 along these boundaries. The fluids are incompressible, the absolute permeability and porosity is constant, and each fluid has its own constant mobility. Thus, the pressure satisfies Laplace's equation in each region. Across the interface, pressure is continuous and the normal component of fluid flux is 1. These conditions are shown in Fig. 1. The velocity of a point on the interface in the direction of the normal from Fluid 1 into Fluid 2 is U,/ Q, where Un is the normal component of volumetric flux at the point on the interface, i.e., For brevity, we call the problem defined above "Problem A". Problem A is a simple example of a dynamical fluid-fluid interface problem. However, the same numerical methods which we use to solve Problem A can be extended to the solution of a large number of fluid-fluid interface problems which are mathematical models for various oil recovery processes,l hence our interest in Problem A. We define the interface by prescribing the x, y coordinates of a finite set of points. These points are called "interface mesh points" and are illustrated by triangles or asterisks in the figures. Fig. 2 is a procedural (flow) chart displaying the main steps in the solution. We comment briefly on some of these steps in this section and then give further details in subsequent sections. For mobility ratio greater than one it is well known that Problem A is unstable.*2 Small amplitude,

Jan 1, 1965

By W. F. Holbrook

In a previous paper1 a method for the measurement of the comparative desulphurizing power of slags was described and data were presented covering the range of likely slags containing up to 10 per cent MgO. In the present work the range is extended to include slags containing up to 20 per cent MgO, and the effect of temperature on 5 per cent and 15 per cent MgO slags over the range 1475' to 1525' C. is included. The method used was that described in the previous paper except that some of the temperature measurements were made with a noble-metal thermocouple instead of a tungsten-graphite thermocouple. Twelve-gram charges of 0.8 per cent sulphur-metal and 5-gram charges of slag were subjected to heating for 30 min. at a prescribed temperature. The charges were analyzed for sulphur content. For purposes of comparison, desulphurizing power is defined as the ratio of the percentage of sulphur found in the slag to that found in the metal. Six slag and metal charges were made coincidentally in 5/8in. holes in a section of an electrode graphite rod. One slag and metal charge was used as a control by means of which adjustment in the desulphurization value could be made for small variations in temperature and other factors. For convenient presentation of the data, the slags are arranged in groups in each of which one of the four main slag components is constant. Thus, the 15 per cent MgO slags are presented separately from those containing 20 per cent MgO. Slags with Magnesium Oxide Constant 15 Per cent Mg0.—The data on slags containing 15 per cent MgO cover a composition range of 24 to 50 per cent SiO2, 5 to 27 per cent A1203 and 24 to 53 per cent CaO. Variation in composition has been in steps of 2 per cent over much of the area. Because the change in desulphurization power is generally gradual with gradual change in composition, certain sections have been covered in steps of 4 per cent and even

Jan 1, 1938

By W. F. Holbrook

In a previous paper1 a method for the measurement of the comparative desulphurizing power of slags was described and data were presented covering the range of likely slags containing up to 10 per cent MgO. In the present work the range is extended to include slags containing up to 20 per cent MgO, and the effect of temperature on 5 per cent and 15 per cent MgO slags over the range 1475' to 1525' C. is included. The method used was that described in the previous paper except that some of the temperature measurements were made with a noble-metal thermocouple instead of a tungsten-graphite thermocouple. Twelve-gram charges of 0.8 per cent sulphur-metal and 5-gram charges of slag were subjected to heating for 30 min. at a prescribed temperature. The charges were analyzed for sulphur content. For purposes of comparison, desulphurizing power is defined as the ratio of the percentage of sulphur found in the slag to that found in the metal. Six slag and metal charges were made coincidentally in 5/8in. holes in a section of an electrode graphite rod. One slag and metal charge was used as a control by means of which adjustment in the desulphurization value could be made for small variations in temperature and other factors. For convenient presentation of the data, the slags are arranged in groups in each of which one of the four main slag components is constant. Thus, the 15 per cent MgO slags are presented separately from those containing 20 per cent MgO. Slags with Magnesium Oxide Constant 15 Per cent Mg0.—The data on slags containing 15 per cent MgO cover a composition range of 24 to 50 per cent SiO2, 5 to 27 per cent A1203 and 24 to 53 per cent CaO. Variation in composition has been in steps of 2 per cent over much of the area. Because the change in desulphurization power is generally gradual with gradual change in composition, certain sections have been covered in steps of 4 per cent and even

Jan 1, 1938

By Robert C. Linares

Cubic zinc sulfide has been grown from molten salt solutions substantially below the hexagonal-cubic phase transition of 1020°C. Crystals free of birefringence have been grown from molten lead chloride at temperatures from 500° to 800°C. Factors affecting the optical transmission and the birefringence are discussed. CUBIC zinc sulfide is of interest for electrooptic devices and as an optical coating material. However, it cannot readily be produced as large crystals which are free of birefringence. The birefringence arises from the fact that the cubic ZnS is usually grown as the high-temperature hexagonal phase and is transformed to the lower cubic phase by annealing.' This results in stacking faults, stress, and birefringence. A requirement for the growth of cubic ZnS is that it be grown below the phase transition of 1020°C.2 Crystals of cubic ZnS have been grown below 1020°C by the hydrothermal,3 flux,4 and vapor transport5 techniques. However, these all appear to have limitations in size or quality of material produced. It was felt that a new flux method might have a good chance of overcoming some of the previous problems. Mita6 reported the growth of hexagonal ZnS from molten NaCl and wilke7 reported the growth of iron sulfides from molten lead chloride solution, indicating that molten chlorides make good solvents for sulfides. An investigation of a number of possible molten chlorides as solvents showed that molten PbCl2 has an appreciable solubility for zinc sulfide and that crystals can be grown at temperatures from 500° to 800°C. EXPERIMENTAL Crystal growth was performed in open or sealed Vycor or fused silica tubes, in an argon atmosphere or vacuum. There were no deleterious effects due to using vacuum; however, a sealed essentially isothermal system must be used to prevent vapor transport mechanisms from dominating. This will be discussed later in detail. Noble metal containers were not usable as they were severely attacked by these melts. The materials used were: reagent-grade PbC12, reagent-grade ZnS, optical-coating-grade ZnS, and Irtran 2 (ZnS). Crystal growth was accomplished by both slow cooling techniques and gradient growth techniques. In the slow cooling techniques, 15 g of ZnS and 100 g of PbCl2 were used. The components were placed in the silica tube, heated at 800°C for 2 hr, and then slowly cooled (l° to 10° C per hr) to 500°C. The furnace was constructed so that the tube could be inverted, thus allowing the liquid to drain off the crystals at the end of the run. The gradient runs were made by placing the above mixtures in a silica tube at 550° to 600°c, Fig. 1. A temperature gradient was maintained such that the floating mass of undissolved sulfide was 10° to 50°C warmer than the bottom of the tube. Growth occurred on spontaneously nucleated sites at the cooler bottom. RESULTS When using high cooling rates (5° to 10°C per hr), crystals form in thin sheets perpendicular to the {111} face. Crystals 5 by 5 by 1.2 mm, Fig. 2, have been ob-

Jan 1, 1969

By L. W. McKeehan

THE occurrence of twins in large ferrite crystals, made by a new process, was reported in a recent note.1 This paper describes a typical case of such twinning and suggests, on the basis of the observed facts, why smooth slip-planes are rarely observed in this metal. METHOD OF PREPARATION The material in. which the crystals here dealt with were grown was made from 1/8-in. Armco iron welding rod containing C, 0.04; S, 0.037; P, 0.003; Si, 0.008, and Mn, 0.02 per cent. This rod was cold drawn into wire about 1 mm. dia. A piece of this wire was supported vertically and was locally heated in hydrogen at atmospheric pressure to about 1400° C. by an alternating current (60 cycles per sec.) of about 35 amp., passed through it between a pair of traveling contacts about 8 cm. apart. The rate of travel for the case in hand was 12 cm. per hr. After some 30 cm. of the length of the wire had been heated and cooled in this manner the whole wire was immersed for a few seconds in dilute nitric acid, not restrained by alcohol. Etching was continued until, ass nearly as could be judged by eye, the original smooth cylindrical surface of the wire was no longer capable of specular reflection. MEASUREMENTS The wire in the etched state was next mounted in a goniometer of special form which allowed the measurement of the spherical coordinates of the normals to any plane surfaces left by the etching. These coordinates were most conveniently a polar distance, ?, from one direction of the wire axis, and an azimuth or longitude, [ø], from an arbitrary prime meridian. The region to be described more particularly is shown at a low magnification in Fig. 1, which gives two different views, differently illuminated to show the spatial relationship of a crystal occupying most. of the part shown and of an inclusion, or rather a series of three inclusions suspected of being twins based on the principal crystal.

Jan 1, 1928

By C. H. Li, R. J. Stokes, T. L. Johnson

The effect of alumina particles on the nucleation and growth of cracks through a silver- chloride matrzx has been investigated. It has been found possible to promote fibrous cracking in dispersion-strengthened silver, chloride under notch-impact conditions at temperatures at which silver chloride alone cleaves brittlely The modification) of fracture beIzavzor is thought to be due to the relaxation of hydrostatrc stress beneath a notch by the nucleation of cavities near alumina particles. In recent years, composite or dispersion-strengthened materials have been studied primarily to understand their high resistance to plastic flow particularly at elevated temperatures. Dislocation models have been developed with which it is possible to deduce with fair success the effects of interparticle distance, particle size, temperature, upon yielding and creep behavior.l-4 Much less attention has been paid to the fracture behavior of these materials (with the notable exception of common structural steels) and little is known experimentally about the manner in which inclusions affect the nucleation and growth of cracks through a matrix. Nevertheless a beginning has been made in connection with fibrous cracking in ductile matrices where inclusions appear to play an essential ro1e.5-7 During the severe localized plastic deformation which accompanies necking in a tensile test, cavities are believed to develop at inclusions; these cavities subsequently grow and coalesce by plastic flow until separation is complete. It is of interest to consider whether inclusions can affect fracture behavior under loading conditions which restrict the plasticity of the matrix itself (for example, cleavage under conditions of a high imposed strain rate at low temperatures). It is particularly interesting to study these effects in a solid which shows a spectrum of behavior ranging from fully ductile to semi-brittle behavior. Such a solid is silver chloride whose mechanical behavior depends sensitively upon temperature and strain rate.'," The present paper is concerned with a study of the influence of inclusions (in the form of alumina particles) on the fracture behavior of silver chloride loaded uniaxially at low strain rates at room temper- ature and also under notch impact conditions over a wide range of temperature. In particular, it will be shown that the alumina particles can exert a startling effect on the ductile-brittle transition temperature of notched silver chloride and that the magnitude and nature of the effect depends upon both the quantity of alumina and the shape of the alumina particles. 1. EXPERIMENTAL PROCEDURE 1.1 Materials Used. Silver chloride powder of analytical reagent (AR) quality having an average particle size 6 was supplied by the Mallinckrodt Chemical Works (st. Louis, MO.). Acid washed 900 mesh alumina powder, designated A38-900, was supplied by the Norton Co. (Cambridge, Mass.). This powder was added to silver chloride in two forms: a) the as-received condition in which the individual particles were of random irregular shape; their statistical average size was 7; b) in a condition in which each particle was spherically shaped by a fusion technique. In this case, the statistical average particle size determined with the optical microscope was approximately the same (about 5p) but electron micrographic evidence indicated that many ultra fine particles were present in the spheroidized powder. 1.2 Preparation of Composite Materials. Silver chloride-alumina composites containing 2.5, 5, and 15 pct by volume of alumina were produced by the extrusion of mechanically mixed powders blended in a ball mill for 24 hr at room temperature. The mixtures were compacted at 50,000 psi at room temperature in the form of billets 3/4 in. in diameter and 1 in. long which were then extruded with a 16:l reduction ratio at 370°C through a radius-type steel die having a 5 deg lead-in angle. An extrusion temperature of 370°C was selected to ensure that all composites had sufficient plasticity to be extruded. Apart from this general requirement, the choice was arbitrary. 1.3 Microstructure of Composites. Attempts were made to check the distribution of alumina metallo-graphically by polishing transverse and longitudinal sections of the extruded rod. Specimens were wet-ground to 600 emery paper and lapped successively with 5 and 0.25-p grades of diamond paste. They were etched for 10 sec in 10 pct sodium thiosulfate solution and lightly polished in concentrated ammonium hydroxide. The most effective way to render the alumina particles and grain boundaries visible was to radiate the surface with intense white light to decorate the grain boundaries and the particle-matrix interfaces photolytically.

Jan 1, 1962

By T. L. MacKay

Oxidation rates of single-crystal and poly crystalline zirconium in oxygen at temperatures from 307° to 815°C obey the parabolic rate law for short ex-posure time, 4 to 6 hr. The activation energy for the oxidation of single-crystal zirconium between 420° and 790°C is 42.6 ± 0.7 kcal per mole, and in the temperature range 307" to 600°C the activation energy for oxidation of poly crystalline zirconium is approximately the same. The high-activation energy is indicative that diffusion through the bulk oxide film is the primary mode of mass transport for both types of metal. The higher oxidation rates for poly -crystalline zirconium in this temperature range were attributed to differences in the orientation of the grains in the metal with respect to the oxidizing surfaces. Above 600°C, vain growth was observed in polycrystalline zirconium, and the oxidation rates approached those of single-crystal zirconium. ThE kinetic data of previous oxidation studies1-' of zirconium in oxygen have been interpreted by both parabolic and cubic rate laws. There is some evidence that there is a transition from the parabolic to the cubic rate law at prolonged exposures, but the question is still controversial. For the parabolic rate law activation energies are reported in the range 18.6 to 35 kcal per mole, and for the cubic rate law in the range 38 to 47 kcal per mole. So far as the mechanism of zirconium oxidation is concerned, inert marker studies10,11 have indicated that the oxidation proceeds by oxygen (anion) diffusion through the oxide film toward the metal-metal oxide interface. Pemslerl2 observed that the orientation of the grains in the zirconium metal substrate affected the rate of formation of the oxide film on the surfaces of the grains and that the orientation dependence of the corrosion rate persisted beyond the initial stages of reaction. The rate of oxidation was a minimum when the c axis of the grain was parallel to the surface of the sample, and rose to a maximum when the c axis was inclined at about 20 deg to the plane of sample surface, and decreased again at higher inclinations. cox13 observed that in 300°C steam a thin oxide film was formed initially on zirconium and that this oxide film, which exhibited interference colors, became dark first along the grain boundaries and then over the whole surface in an inhomogeneous manner as the film thickened. Cox proposed a mechanism in which oxygen diffused along preferred paths created by grain boundaries in the metal and formed a much thicker film at or near the grain boundary than on the central zone of the grain. In the present study, the oxidation rates of single crystals of zirconium were measured in oxygen and compared with the oxidation rates of polycrystalline zirconium of the same bar stock. It was felt that such a comparison would elucidate the role of grain boundaries in the metal substrate. SAMPLE PREPARATION Single crystals of zirconium were prepared by following the procedure of I3apperport,14 starting with 1/4-in. rod purchased as crystal-bar zirconium. Zirconium rods 2 in. long were wrapped in tungsten foil and sealed in quartz tubes at pressures of less than 10-6 mm of mercury. Large single crystals were grown by thermal cycling above and below the a-/3 transformation temperature, 862°C. Several specimens were simultaneously subjected to the same cycling procedure, heating to 1200°C, holding for 4 hr, then cooling in the furnace and holding at a temperature of 840°C for 5 to 10 days. This cycle was repeated five or six times for each set of specimens. The grain size of the crystal-bar zirconium before thermal cycling was between 10 and 30 p. Fig. 1 shows the microstructure of an end section of as-received crystal-bar zirconium. A longitudinal section of each zirconium rod after thermal cycling was polished and examined under polarized light, see Fig. 2, and the largest single crystals were selected for this study. Zirconium rods 1/8 in. in diameter and 1/2 in. long with spherical ends were machined from the single crystals and from the as-received bar stock. An X-ray examination showed that the c axis of the single crystals made either a 34-deg or an 89-deg angle with the rod axis. The specimens were chemically etched for 2 min in solution consisting of 15 parts hydrofluoric acid (48 pct), 80 parts nitric acid, and 80 parts water. The chemical polish removed 1 to 2 mils from the surface. EXPERIMENTAL The Sartorius vacuum microbalance used in this study has a sensitivity of 0.5 pg and a capacity of

Jan 1, 1963

By W. H. Adams

At the present time all the larger and better chemical works of Europe and the United States have introduced, as essential factors in the economical manufacture of sulphuric acid, both Glover towers and Gay-Lussac absorbing columns. The clear exposition of facts given by Bode and Lunge in their very valuable technical contributions since 1870 has slowly but surely brought about radical changes from the old methods of manufacture ; but while the Gay-Lussac column has been known since 1827 and the Glover tower was originated in 1869, yet no theoretical treatise covering the subject fully was given to the world until 1876, when the various contrivances for demonstrating nitrous vitriol were described and criticized by Fr, Bode in a paper "On the Glover Tower" which obtained the great prize of the Berlin Society for the Promotion of Industry.*

Jan 1, 1887

By Fred Wise, C. W. Wark

THE Getchell mine, a comparatively recent gold discovery, is in the old Potosi mining district, Humboldt County, Nevada. All ore is mined from open pits using Diesel shovels and gasoline trucks. Two types of ore are mined, oxide and sulphide. Oxide ores are siliceous or shaly; sulphide ores either gougy, siliceous or shaly. In mining, the sulphide ore is segregated into hard and gougy ore, because the gouge must be dried before it can be crushed. The oxide ore is not segregated. GENERAL METALLURGY The oxide ore is the leached outcrop that overlies the sulphide ore body. All of the iron and arsenic sulphides found in the sulphide ores have been thoroughly oxidized. The sulphur and arsenic have been leached out while the iron is present as hematite and limonite. The oxide ore is amenable to direct cyanidation, and although no visible free gold is present it is released at a comparatively coarse grind. The sulphide ore is more refractory, since the gold is all of micron size and some of it is locked in fine sulphides. It has been established microscopically that the free gold is coated with an impervious shell, which is probably some form of iron compound. The sulphide ores contain from 1.5 to 2 per cent of arsenic, which is present as orpiment and realgar with minor amounts of arsenopyrite. The orpiment and realgar are of a later mineralization than the gold and are barren. Roasting and washing of the sulphide ore prior to cyanidation is necessary to eliminate the arsenic, to alter the gold coating from an insoluble form to a soluble form, and to release the gold associated with the fine sulphides. Washing the ground calcine in weak sulphuric acid, trona, or hot water are beneficial in the order named, but to date the water is the best from an economic standpoint. Metallurgical tests as well as plant practice indicate that a certain amount of gold cannot be recovered even by going beyond economic practices. On this basis metallurgical results are viewed in the light of an optimum tailing rather than a percentage of extraction. MILLING PRACTICE Crushing (Fig. 1).-There are three primary ore bins, one each for oxide ore, gougy sulphide ore, and hard sulphide ore. In front of each bin a substantial yard is maintained, which makes it possible to stockpile 2500 tons of oxidized ore, 1000 tons of hard sulphide ore, and 1000 tons of gougy sulphide ore. The bins are fed by a 60-hp. caterpillar bulldozer from the stockpiles. Fig. 1 shows the method and

Jan 1, 1940

By Nathaniel Arbiter

There is a history in all men's lives, Figuring the nature of the times deceas'd, The which observ'd, a man may prophesy, With a near aim, of the main chance of things. W. Shakespeare, Henry IV; Part 2 Introduction This nation's first century embraced two stages of the Industrial Revolution. During one, what had been a colonial agricultural economy began to industrialize; water power, then steam after 1794, were the energy sources; coal and iron were the essential ingredients. The second stage started after 1850; aided by rich and diverse mineral resources, the country began its transition from the Iron Age to the Age of Metals. Early civilizations had been built on stone, and fairly high levels were sustained on iron. But the spectacular advances in the past century in communication, in construction, in transportation by sea, rail, land and air, and in much that characterizes modern civilization have depended increasingly on the use of the complete metallic and nonmetallic resources of the earth's crust. Thus it was appropriate to define the Industrial Revolution as “the period during which man's relationship to natural resources became utterly changed”, 1 with minerals playing a major and indispensable role. But we are now becoming aware that the relationship of man to natural resources must change again. On every hand the dangers inherent in the contamination of land, sea and air by the wastes of civilization are becoming apparent. And from the growing realization that mineral wealth is finite must eventually come other far reaching changes in mineral use and distribution. For on the scale of centuries we cannot continue to exploit mineral resources even at present rates, let alone at expanded rates, without eventual depletion of the more abundant resources, and early exhaustion of the less abundant. In the past our problems were relatively easily met by the development of new and improved machinery and processes. But the future will

Jan 1, 1971