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By Alfred V. de Forest

We are now assembled in this hall for the eighteenth lecture in honor of the memory of our greatest American metallurgist, Henry Marion Howe. Many of his most intimate contemporaries, led, as was fitting, by Professor Sauveur, have described his vital accomplishments in three fields: as a leader in technical industrial development; in theoretical research; and finally as a teacher and source of inspiration for nearly two generations of students. In 1914 Professor Howe had retired from active teaching, but maintained his laboratory at Columbia University under the care of Arthur G. Levy, with whom he published many of the papers that later were incorporated into his last book, " The Metallography of Steel and Cast Iron." My position at the time was that of personal assistant to Professor Campbell—no pay, no duties, but the great privilege of preparing specimens, taking pictures and attending to some of the current consulting work. Whenever possible, I visited Howe's laboratory to chat with Levy and gather ideas about the wonderful field of metallography—in which I was a rank amateur, rescued by the quiet enthusiasm of Donald Smith of Princeton from an instructorship in civil engineering. Levy let me act as a fly on the wall during the Professor's occasional visits. Busy as he was, Professor Howe took the time and trouble to encourage my interest, as he had done for hun- dreds of others. He told me how he went about gathering his own information speculating as to causes, considering experiments, and verifying his conclusions. I ventured to mention some tests I had run on the irregular stretching of wires of different metals. He read the small volume I had prepared of ill-assorted facts and fancies and remarked: "Nobody cares for your theories or the history of your tests. Describe what you found as briefly as possible and perhaps I can help you to publish." Curiously enough, among my discards were some autographically recorded load-versus-electrical-resistance measurements. Taken with inadequate knowledge and equipment, these curves did not reproduce consistently, but if the relationship between strain and resistance had then been explored, the latest type of strain gauge might have been in useful service for the past 25 years. Professor Howe was a gifted teacher, perhaps because he was primarily an ardent and assiduous student. His own eagerness to learn and his willingness to revise and extend his opinions constantly encouraged those of his environment to be diligent and painstaking in the pursuit of knowledge. In honoring his memory, I also wish to bring to mind the kindly, humorous and quiet Levy, and join his name again, as it was for too brief a space in the past, with that of many-sided Henry Marion Howe. Factors oF Impact Strength The subject chosen for the Howe Memorial Lecture by Dr. Gillett last year

Jan 1, 1941

By F. N. Rhines, T. E. Leonitis

The oxide scale that forms upon magnesium at elevated temperatures is non-protective in the sense that the rate of oxidation is constant and thus does not decrease with the growth of the scale as it does with other common metals. This generality was first stated by Pilling and Bedworth' and has been verified by Suzuki2 and by ScheiL3 Pilling and Bcdworth argued that the nonprotective characteristic could be predicted from the fact that magnesium oxide occupies less space than does the metal from which it springs, wherefore the scale is not expected to cover the metal so completely as to exclude all direct access to the atmosphere. Linear oxidation is thought by Scheil to be common to all cases where the reaction occurs at the oxide-metal interface. According to Suzuki," he product of high-temperature oxidation in the air is MgO contaminated with no more than traces of a nitride. When the metal is allowed to burn freely a fume composed of cubic crystals of Mg04 is given off. Delavaults observed that excrescences form upon liquid magnesium and alloys in thc course of oxidation. Beyond this it is known that the use of atmospheres containing small quantities of sulphur dioxide6 or carbon dioxide serve to retard the oxidation of solid magnesium and that beryllium' and calciums minimize the oxidation of molten magnesium exposed to the air. Many studies have been devoted to the nature and rates of "protective" oxidation, as exemplified by the cases of copper and iron, wherein the rate is characteristically parabolic. The theory of parabolic oxidation is well developed.~ Linear oxidation, on the other hand, has received but little attention and the theories proposed by Pilling and Bedworth and by Schcil have yet to withstand careful examination. There exists no comprehensive survey of the high-temperature oxidation of magnesium (or of any other metal that exhibits linear oxidation) over a broad range of temperature, under a variety of atmospheric conditions and covering a large group of alloys. It has been the purpose of the present investigation to provide such a survey, with the object of gaining a fuller understanding of linear oxidation, especially as applied to magnesium. Experimental Procedure and Results The experimental studies undertaken were of two kinds: (I) measurement of the rate of oxidation as influenced by the 6c

Jan 1, 1946

By C. A. Zapffe

BOTH the foundryman and the theoretical metallurgist are now generally agreed that the anomalous "rising" or "bleeding" of certain ferrous castings of killed metal is primarily attributable to hydrogen. How and why the phenomenon occurs, however, have not been made clear. The following discussion is intended to harmonize foundry experience with metallurgical theory so that the foundryman may possibly improve his ability to prognosticate whether a certain casting may bleed or not. BLEEDING, RISING, AND PIPING The "rising" to be discussed here is not to be confused with the action in rimming ingots as a result of the carbon-oxygen reaction, although a conclusion will be drawn that may apply to the art of controlling the rimming action. Only killed metal is considered, which includes both steels and irons. In Fig. I, three killed, chill-cast ingots are shown: a porous ingot whose evolution of gas during late stages of solidification has ejected metal through the top; an ingot in which moderate gas evolution during solidification has lifted the mushy central metal, i.e., it has "risen"; and, third, a sound ingot with good piping characteristics. The first type is referred to as "bleeding," and generally infers that a solid skin had first formed through which the liquid metal later erupted. There is no fundamental distinction between bleeding and rising in reference to killed metal.* POROSITY Hydrogen appears as a cause of bleeding because the gas evolution simultaneously leaves a porosity of a type traceable to hydrogen. Twenty years ago, Melmoth1 noted that killed steel that rose unexpectedly in the mold, if returned while liquid to the furnace and heated further under a reducing lime slag, would again rise in the mold; but that if the ingot were allowed to solidify and was then remelted no rising occurred. A critical quantity of the responsible gas is therefore removed by the rising action. Melmoth associated rising with high silicon (0.7 to 0.9 per cent) and concluded that silicon increased gas absorption. Because silicon is a strong deoxidizer, oxygen must, therefore, be eliminated from consideration of the three common gases in steel-oxygen, nitrogen, and hydrogen. Butterworth2 later decided that pinhole porosity was caused by gases dissolved in the metal and that hydrogen was obtained from steam in the mold. Allen's classical work on copper castings,3 soon followed by

Jan 1, 1942

By T. E. Leonitis, F. N. Rhines

The oxide scale that forms upon magnesium at elevated temperatures is non-protective in the sense that the rate of oxidation is constant and thus does not decrease with the growth of the scale as it does with other common metals. This generality was first stated by Pilling and Bedworth' and has been verified by Suzuki2 and by ScheiL3 Pilling and Bcdworth argued that the nonprotective characteristic could be predicted from the fact that magnesium oxide occupies less space than does the metal from which it springs, wherefore the scale is not expected to cover the metal so completely as to exclude all direct access to the atmosphere. Linear oxidation is thought by Scheil to be common to all cases where the reaction occurs at the oxide-metal interface. According to Suzuki," he product of high-temperature oxidation in the air is MgO contaminated with no more than traces of a nitride. When the metal is allowed to burn freely a fume composed of cubic crystals of Mg04 is given off. Delavaults observed that excrescences form upon liquid magnesium and alloys in thc course of oxidation. Beyond this it is known that the use of atmospheres containing small quantities of sulphur dioxide6 or carbon dioxide serve to retard the oxidation of solid magnesium and that beryllium' and calciums minimize the oxidation of molten magnesium exposed to the air. Many studies have been devoted to the nature and rates of "protective" oxidation, as exemplified by the cases of copper and iron, wherein the rate is characteristically parabolic. The theory of parabolic oxidation is well developed.~ Linear oxidation, on the other hand, has received but little attention and the theories proposed by Pilling and Bedworth and by Schcil have yet to withstand careful examination. There exists no comprehensive survey of the high-temperature oxidation of magnesium (or of any other metal that exhibits linear oxidation) over a broad range of temperature, under a variety of atmospheric conditions and covering a large group of alloys. It has been the purpose of the present investigation to provide such a survey, with the object of gaining a fuller understanding of linear oxidation, especially as applied to magnesium. Experimental Procedure and Results The experimental studies undertaken were of two kinds: (I) measurement of the rate of oxidation as influenced by the 6c

Jan 1, 1946

By D. A. Thomas, M. F. Comerford

Poly crystalline wires of Fe-3.2 wt pct Si were cold-drawn to 31, 66, and 87 pct reductions of area. Mechanical properties and tnicrostructures were studied after recovery and re crystallization. An initial increase in strength during recovery was ascribed to strain aging, and subsequent softening was largely due to polygonization rather than re-crystallization. No unique actioation energies could be determined for the recovery process. Rather, activation energies ranged from 60,600 cal per mole at 10 pct recovery to 83,200 cal per mole when recovery was 50 pct complete. Sites for the nucleation of recrystallization were found to depend on time and temperature. In the early stages of re-crystallization, nucleation occurred in deformation hands. Later, or at high temperatures, recrystal-lized grains were nucleated primarily al grain boundaries. Polygonized structures did not seem to be preferred sites for nucleation. MUCH of the research on deformation, recovery, and recrystallization processes in bcc materials has been performed on single crystals or lightly worked polycrystals. Little study has been devoted to the relation of mechanical properties to micro-structure in polycrystals after severe deformation and subsequent annealing. This paper presents the results of a study of the tensile properties and microstructures of Fe-Si wires drawn varying amounts and annealed at a series of temperatures. EXPERIMENTAL PROCEDURE The experiments were carried out on an alloy of the following composition: 3.2 wt pct Si, 0.08 Mn, 0.016 C, 0.005 0, 0.0002 N, 0.0001 H, 0.008 P, 0.034 S. The material was received as l-in.-sq bars cut longitudinally from a hot-rolled slab provided by the Armco Steel Corp. The bars were forged to 3/8-in. rounds, centerless-ground to 0.250 in., and swaged to '0.108 in. All subsequent reductions were performed by room-temperature wire drawing at the rate of 2 in. per min. Each preliminary draft gave approximately 30 pct reduction of area and was followed by a l-hr anneal at 1010°C in dry hydrogen. Three lots of wire were made with ultimate cold reductions of 31, 66, and 87 pct reduc-

Jan 1, 1965

By Frederic E. Carter

THERE have been many attempts to prove that platinum was known to the ancients, but since no traces of the metal have been found in the relics of early times, it must be concluded that it was not known to them. As far as records go, it was actually first discovered in the 16th century in a Spanish mine on the Pinto River in South America; from which source it received its name of Platina del Pinto (little silver from the Pinto). It was more or less of a rarity and was a subject of interest to a few chemists only, until the year 1822 when the metal was first discovered in Russia. In 1819 there were noticed in the washings of the gold sands of the southern part of the Ural Mountains, grains of a heavy white substance, but it was not until three years later that this substance was found to contain platinum. While at first the amounts of platinum brought from the Urals were meager, prospecting soon disclosed rich deposits extending over a considerable area, and nuggets from 10 to 20 lb. were by no means rare. This discovery assured to chemists an ample supply of platinum for their crucibles, etc. The ore is now found in various parts of the world but the richest deposits are still found in the Ural Mountains. The platinum of commerce is obtained entirely from alluvial deposits at depths varying from 6 to 40 ft. The sand and gravel of former river beds are subjected to a series of screenings and washings to effect the separation of the ore. Actually, probably all gold-bearing gravel beds of the world contain platinum, and it is more than likely that large quantities of platinum ore have been thrown away with the black sand washings from gold placer deposits. This is especially true of the alluvial deposits of the Pacific Coast in California and Oregon. Platinum ore is usually found in the form of rounded or flattened grains of "sand," and occasionally in irregular lumps of the size of peas. Large nuggets are very rare. The ore has a metallic luster and is distinguished by its steel gray color, but shows light gray streak when rubbed on a hard white surface; it has a high specific gravity, 16 to 19; is infusible in the hottest blast furnaces, and insoluble in any single acid. Platinum ore is a complex body consisting of the metal in combination with varying proportions of the other members of the platinum group; iridium,

Jan 1, 1928

By H. C. Johnson, J. K. Elliott

One of the primary requirements for successful operation of an enriched gas-drive project is to control the composition of injection gas. This can become a serious and difficult problem, particularly in cases where the enrichment material is being furnished from a number of field -produced gas streams. It is possible to effect control of the injection gas composition through frequent or continuous sampling; however, this can be extremely costly and, in many cases, impractical due to laboratory requirements of time. Another alternative would be to provide a calculation technique which would be flexible and sufficiently accurate to predict composition of the liquid and gas streams of interest at any point in the system. The purpose of this paper is to discuss a technique that was used successfully on an operating enriched gas-drive project for developing information which could be used for controlling composition of the injected gas. FIELD OPERATIONS The particular field (hereafter called Example field) in the example operation being discussed is composed of four oil reservoirs (A. B, C and E) and one gas condensate reservoir (D). Casinghead gas from the oil reservoirs and gas from the gas condensate reservoir are gathered through a field gathering system as shown in Fig. I for injection into Reservoir C. The gas mixture which is recovered from the five reservoirs for injection purposes is composed of gases liberated in 19 individual separators, each operating at a separate temperature and pressure. PROPOSED CALCULATION TECHNIQUE It is well known that vapor-liquid equilibrium calculations in general use throughout the petroleum industry can be used to predict reliably the phase behavior of hydrocarbon mixtures, particularly at pressures less than 1,000 psig. It is then a simple matter to account for the material on a ComPonent basis by m''ing flash and material balance calculations at each separation point in a hydrocarbon system. Accordingly, it was proposed to use vapor-liquid equilibrium and material balance cal- culations with a medium-sized electronic digital computer as a basis for developing a control procedure for use in controlling injection gas composition in the enriched gas-drive project. Although the approach is a simple one, the numerous vapor-liquid equilibrium calculations involved make the problem laborious; in this particular case, it would have been impractical to make sutficiently complete analysis without the aid of digital computing equipment. SAMPLING AND VERIFICATION OF CALCULATION PROCEDURE To obtain representative gas and liquid stream samples and to provide a quantitative measure of overall system Performance for comDarative purpLses, a thorough test of the field and plant system was conducted in the summer of 1957. Oil production at each battery was sta-

By A. S. Nowick, E. S. Machlin

ONE of the main criteria used to rate the heat-resisting properties of alloys is stress rupture.1 During a stress-rupture test a tensile specimen is held under a constant load at a constant temperature until it fractures. The chief measurement made during this test is the time required for rupture at the specific test stress and temperature. It was found empirically from a series of stress-rupture tests at a constant temperature that when the logarithm of the time for rupture is plotted against the logarithm of stress a straight line is obtained within experimental error.2~3 This method of showing stress-rupture data has been adopted by many investigators and the KACA.4 By interpolation and extrapolation from these plots, values of the stresses required to rupture the specimens (the rupture strengths) in 10, 100, and 1000 hr are obtained for specific temperatures. Alloys are then rated for a particular application on the basis of their rupture strengths at the rupture life that most nearly represents the application. Inasmuch as stress rupture is an important criterion in rating heat-resisting alloys, it would be advantageous to know the quantitative dependence of the time for rupture on stress, temperature, com- position, and structure. In order to obtain this information, an investigation was made at the KACA Cleveland laboratory during the spring of 1945. The theory of rate processes was used because it has been found to apply to certain processes such as chemical reactions, viscous flow, and creep that occur at a definite rate for given conditions. It was thought that stress rupture was such a process. An equation was derived that gives, for a given com- position and structure, the dependence of the time for rupture on stress and temperature. The investigation is part of a general program to provide information that will lead ultimately to the development of better alloys in order that the efficiency and power output of gas turbines used in aircraft propulsion can be increased. THEORY The theory of rate processes will first be discussed as a general theory. It will then be shown that if stress rupture of heat-resisting alloys can be treated as a rate process, certain equations must be satisfied. Later sections will then show that these equations are satisfied. General Theory of Rate Processes The theory of rate processes5 eveloped by Eyring and others has been applied to chemical reactions as well as to other processes such as viscosity of liquids and diffusion. In every case in which rate- process theory can be applied, there is a small subdivision, so that the macroscopic process is the net effect of all the small processes. This smallest subdivision is called the "unit process.'' For example, in a chemical reaction the unit process is

Jan 1, 1947

By Frank L. Gaddy

Falls of roof account for over 50% of the fatalities that occur in coal mines in the U.S. Thus, roof control is one of the more important phases of underground mining. In reality, the control of roof influences the system of mining and is a major determinant of the width and spacing of working places, operations at the mining face, ventilation control, and surface subsidence. Frequently, the control of roof is the largest single cost item. Roof control is a never-ending task, not only at the working face and throughout sections where men are working, but along haulways and airways that must be maintained for the life of the mine. This is because roof, even the best of roof, slowly deteriorates, so it must be frequently examined, with corrective support applied when needed. As coal is excavated, stresses are set up in the roof became the previous equilibrium is upset, resulting in pressures that cause fractures and slight, movements that are, frequently, hard to detect. Unless the immediate roof, in the excavated area, is given support by artificial means, it might fall or there might be a succession of falls, varying from a thin scale to several feet, depending on the nature of the top. Exceptions to this are those rare mines, or sections of mines, with hard, strong, nonweathering roof that requires no support. GENERAL CLASSIFICATION OF ROOF There are two broad types of roof as far as support is concerned, the immediate roof above the coal and the main roof. Artificial support for mining purposes is only concerned with the immediate roof as nothing except large blocks of solid coal, or massive concrete, will support the main roof. The immediate roof is generally a few feet thick but can vary from inches to 20 ft or more. There are examples of where there is no immediate roof as the massive main roof lies directly on the coal bed, but this is rare. Impossibility of supporting the main roof and all of the cover

Jan 1, 1973

By J. Marshall Downey

The most fortunately situated U. S. potash producer-whether in New Mexico, California, or Utah--once simply took from the ground a mixture of sodium chloride and potassium chloride, crushed it to a maximum of 10 mesh, and separated the two salts by physical methods. He piled the sodium chloride on the desert and sold the potassium chloride to fertilizer mixing companies. Seven companies in the Carlsbad basin of New Mexico now use at least three basic processes for making the separation and at least three more processes have been or are under investigation. In addition, two companies outside the basin use two methods for taking KC1 from natural brines

Jan 12, 1958

By Kenneth E. Gray

The turbulent flow drag coefficients, or friction factors, have been experimentally determined for the cut-tings normally encountered in drilling operations. The gas law and average drag coefficients for characteristically flat particles (limestones and Shales) and for angular to sub-rounded particles (sandstones) were used to extend Newton's equation to a more useful form. The resulting equations are expressions for the slip velocity of a particle as a function of the particle size and shape, the bottom-hole injection Pressure, and the Bottom-hole temperature. The velocities necessary to lift actual rock cuttings as observed in the laboratory were compared with velocities predicted from the derived equations. Results indicate that there is no single correct circulating velocity and that the commonly used 3,000 ft/min linear velocity may he sufficient to lift only very mall particles. The advantage, in terms of horsepower requirements, of cycling high pressure air to obtain lower compression ratios was shown. INTRODUCTION A promising departure from standard rotary hydraulic drilling is air or gas drilling. In many instances the rate of penetration and bit life increases resulting from this method have been very substantial. Further the application of air drilling in areas of lost circulation or water sensitive pay zones has been highly successful. Purpose For the drilling contractor, the practical question remains, "How much air pressure and volume should I have?' lt is necessary to have a reasonable knowledge of the air velocities and pressures required in air drilling operations for the proper design and most advantageous use of surface equipment and for adequate removal of cuttings from the borehole. Eased on experience, most operators agree that at least 3,000 ft/min linear velocity is necessary for satisfactory hole cleaning.' It was the purpose of this investigation to evaluate the drag coefficients, or friction factors, for the cuttings normally encountered in drilling operations, i.e., sandstones, limestones and shales, and to utilize the values obtained to develop an expression for the minimum velocities and pressures (hence the volumes) necessary to lift these cuttings. THEORY Several investigators have done extensive work on the ability of drilling mud to lift bit cuttings. They conclude that the ability of a drilling mud to lift cuttings is dependent on the density difference between the rock being drilled and the drilling mud, the cutting size and shape, the mud flow constants, and the flow state (laminar, transitional or turbulent) of the mud. However, drilling muds are not true fluids but have a variation of viscosity with velocity in laminar flow and a constant apparent viscosity in turbulent flow. A survey of the literature revealed that no experimental work had been done to determine the velocities necessary to lift actual rock cuttings using a compressible fluid such as air or gas. In 1953, Nicolson6 stated that in air drilling fluid mechanics the particles could be assumed spherical in shape and that ; constant drag coefficient of 0.5 could be used due to the highly turbulent flow of the circulating air. By equating the turbulent resistance on the particle to the gravitational force on the particle, he obtained the expression, ^ = 2.67^y ,.......(1) where V, is slip velocity of spherical particle, ft/sec; D is particle diameter, in.; p, is particle density, 1b/ft8; and p, is fluid density, lb/ft3. However, as stated earlier, most operators seem to agree that adequate hole cleaning can be obtained by circulating a sufficient volume of air to give a linear velocity of 3,000 ft/rnin in the annular space. Basic Equation The velocity with which a solid particle freely falls through a fluid will increase until the accelerating force, gravity, is equal to the resisting forces, buoyancy due to the fluid displaced by the particle and friction due to the relative motion of the particle through the fluid. When the accelerating and resisting forces become equal,

By G. G. Reed

G.G. Reed, Jr. The authors are to be commended for finding a material for pellets binding that we were unable to uncover during the investigations that led to US Patent No. 3,748,116, "Method for producing metallic iron powder from iron ore concentrate," July 24, 1973, by G.G. Reed, Jr., J.M. Karpinski, and S.V. Fox. This patent concerns a method of processing "super"-concentrates prepared from magnetite or "blue dust" into molding-grade metallic iron powder for use as a bulk commodity, in contrast to current methods which produce small batches that are custom-blended with additives and/or alloys to customer specifications. The one thing we had not found at that time was an organic binder (mineral-matter-free) that would allow induration to produce hardened pellets that would survive SL/RN Direct Reduction. Peridur appears to provide this missing link needed for large scale (200 t/a, or 220,460 stpy) single line plant capacity consistent with a low market price to ensure greatly broadened use of metallic iron powder. I hope that industry will adopt this combination so that metallic iron powder usage can fulfill its potential. ?

Jan 1, 1986

By G. W. Preckshot, J. W. Gorman

MOLTEN metals offer an excellent medium for the study of molecular diffusion and interphase transfer. In the absence of intermetallic compound formation, solutions of molten metals are solutions of elements. Therefore, complicating factors such as molecular structure, dissociation, association, polarization, and so on, are generally absent. Further, metals remain in the liquid state over a wide range of temperature. Thus, the effect of temperature on transport processes can be studied in more detail. Although some data are available for the diffusion of metals in the molten state at high temperatures,"""".'!' the most useful and accurate data are those for the diffusion of various elements in mercury at room temperature. The effective radius of diffusion for the various elements in mercury may be calculated from the Stokes-Einstein relation.'-These calculated radii are compared with the atomic and ionic radii calculated from X-ray data on crystals." The effective radii of diffusion of the alkali and alkali-earth metals correspond to those of the neutral atom; those of cadmium, silver, lead, zinc, thallium, bismuth, and tin correspond to ionic radii; and those of copper and gold indicate larger radii due to association with mercury or more likely, faulty diffusion data. Independent evidence"' supports the notion that alkali metals are uncharged in amalgams. The concept of metals moving free of their conductance electrons in the liquid state has been discussed by Eyring, et al,'" in connection with studies on the viscosity of pure molten metals. Considering the approximate nature of the tabulated atomic and ionic radii and the variance in the diffusion measurements, the application of the Stokes-Einstein equation to the diffusion of metals in mercury gives gratifying results. It is noted that a number of these metals have article radii eaual to or less than those of the solvent mercury.".'*,"' Soba1,'" sing the inaccurate Roberts-Austin20 data, indicated that the effective radius of diffusion might well be a function of temperature. Additionally in studies of mass transfer between phases, many conflicting opinions have been expressed concerning the assumption of equilibrium at the interface." ,","," The results of the present work on the diffusion of solid copper in molten lead throws light on the tempera- ture variation of the diffusion radius as well as the extent of the interfacial resistance. The theoretical background and experimental procedure are presented here in detail. Results on other systems will be presented in subsequent papers. Nomenclature The following nomenclature is used in the paper: A—cross-sectional area of diffusion column, sq cm C, C,—concentration of solution and saturated solution respectively, g per cc D,D'—-diffusivity, sq cm per sec e—Naperian base h—ratio, k/D k—mass-transfer coefficient, cm per sec L—diffusion column length, cm n—series index q—flux, g per sq cm-sec r—radius, cm or A R—-gas constant t—time, sec T—temperature, K V—volume, cc w—weight of copper-lead alloy on copper cylinder WT—-total copper transferred to lead diffusion, column, g Z—distance from top of diffusion column, cm 2'—distance from copper-lead interface, cm (2' = L-2) u,,—roots of diffusion equation Mathematical Apparatus The model shown in Fig. 1 applies to the diffusion of solid copper into molten lead. Here Fick's first law may be written where all terms are defined in the nomenclature. It is assumed that the volume of the lead column is constant. This is justified since experimental densities compared favorably with calculated densities based on perfect interstitial mixing. Thus there is no counter diffusion of lead. It is clear that 2 in Equation [I] should be measured relative to the interface which moves relative to the diffusion cell but not to the liquid phase. Hence, the frame of reference is the plane of the copper-lead interface. The diffusivity calculated at constant volume, D", is that defined by Hartly and Crank" and is designated herein as D. No Interfacial Resistance—The two situations of the presence and absence of interfacial resistance will be treated. The simplest is the latter which re-

Jan 1, 1959

By P. H. Wendland

Calculations are presented for the design of a silicon photodiode in which the incident light beam makes multiple passes between the detector surfaces. Total internal reflection is used for this "light-trapping" effect. By this means, the optical path length can be extended to several millimeters, while the electrode separation remains less than 102 cm, as required for nanosecond response time. Data are presented for a Schottky barrier photodiode constructed on a multiply reflecting silicon base wafer. It is shown that the long-wavelength response is considerably extended in such structures without a corresponding sacrifice in high-speed response. The development of efficient and powerful lasers at 1.06 p has stimulated interest in detectors which operate at this wavelength. In typical silicon photodiodes, for detecting 1.06 p radiation, the requirements for high speed and high sensitivity are mutually exclusive. Since the absorption coefficient is only 25 cm-', a lo-'-cm path length is required to absorb 92 pct of the incident 1.06 p radiation. If the electrode separation is greater than 10 cm, however, the carrier transit time will be greater than 1 nsec. This problem can be solved by allowing the incident light beam to make multiple passes between the electrodes. The optical path length can then be extended to several millimeters, as required for complete absorption, while the electrode separation remains less than 10' cm, as required for nanosecond response time. In a typical photodiode geometry, one ohmic contact and one rectifying contact are formed on the two opposite surfaces of a base wafer, and the wafer thickness determines the electrode separation. The objective of the multiple reflection design is to allow all 1.06 p radiation to enter the detector front surface and to form the back detector surface so that no 1.06 radiation can exit. Total internal reflection at the back detector surface is well-suited for light trapping of 1.06 p radiation because the relatively large dielectric constant of silicon leads to a critical angle of 16.5 deg for total internal reflection. LIGHT TRAPPING It is well-known that, as light passes from one medium such as air into another medium such as glass or silicon, the angle of refraction is always less than the angle of incidence. In the limiting case, where the incident rays approach an angle of 90 deg with the normal, the refracted rays approach a fixed angle +, beyond which no refraction is possible: this is called the critical angle. It follows from Snell's law that where = critical angle, n - index of refraction of air, n' - index of refraction of the medium. Applying the principle of reversibility of light rays, all internal angles of incidence greater than +, will produce total internal reflection and "light trapping". The index of refraction of silicon at 1.06 p is 3.5,' and the critical angle is thus 16.5 deg. Fig. 1 shows these relationships for silicon. This very small critical angle in silicon is significant because all incident angles between 16.5 and 90 deg will produce total internal reflection and "light trapping". This effect can be implemented with a "prismlike" geometry, so that incident light can be introduced into the sample without loss and "trapped". PHOTOSIGNALS A precise knowledge of the absorption coefficient at 1.06 in silicon is of critical importance to the design of fast and efficient silicon photodiodes for 1.06 radiation. Dash and newman2 show a value of 25 cm-l, and our measurements have corroborated this value. Assuming that the collection of photoinduced minority carriers is perfect, the quantum efficiency of a photodiode is dependent only on the absorption coefficient. It then follows from Lambert's law that where QE is the quantum efficiency in pct, a is the absorption coefficient, d is the optical path length, and the reflectivity at the surface is assumed to be completely suppressed by an optical interference layer. Fig. 2 gives the maximum quantum efficiency for 1.06p radiation of a silicon photodiode with optical path length d, using Eq. [2]. The ultimate response time of a fully depleted photodiode to an incident light pulse can be considered to be the arrival times of all photoinduced carriers at the contacts, i.e., the minority carriers at the junction interface and the majority carriers at the oppo-

Jan 1, 1968

By E. S. Davenport, R. J. Hafsten, R. A. Grange

The influence of austenite grain size upon the hardenability of steel is now fairly well understood; for a given austenite, increasing the grain size increases the depth of hardening, and, since the latter is related to the fundamental transformation behavior of austenite, it follows that austenite decomposition must, in general, be retarded by increasing grain size. To date, very little quantitative information bearing directly on the effect of austenite grain size upon the progress and result of isothermal transformation has been published. Davenport and Bain,' and Zimmerman, Aborn and Bain2 have shown that the transformation is definitely relarded in hypereutectoid plain carbon steels at temperatures near and above the upper region of rapid transformation (Ar') when the austenite grains are increased in size. More recently, Griffiths. Pfeil and Allen3 investigated the effect of a series of different heating (austenitizing) temperatures upon the progress of isothermal transformation at 1245°F. (675°C.) and 745ºF. (395°C.) in a medium carbon, low-alloy steel; while they reported no measurements of the austenite grain size, their results suggest that increase in grain size retards austenite transformation at 1245ºF. (675°C), but has no appreciable effect at 745°F (395°C.). The present paper deals with the results of a study of the isothermal transformation of austenite in a single commercial alloy steel in which a fine-grained or a coarsegrained state was induced by appropriate selection of austenitizing temperature. The data are presented in the form of isothermal transformation diagrams, which clearly show that coarsening the grains lessens the rate of transformation of austenite to proeutectoid ferrite and pearlite—that is, at temperature levels above about 1000°F. (540°C.)—but is without significant effect at lower temperatures where the transformation product is bainite or martensite. It is to he presumed that the foregoing statement would be valid, at least in principle, for many other grades of steel; it confirms again that the mechanism of transformation to a pearlitic structure is fundamentally different from that to an acicular structure. A number of related observations were made, which seem to throw some light on the transformation process as it takes place in alloy steels, particularly at temperature levels in the vicinity of 1000ºF. (540°C.), where the transition from lamellar to acicular structures occurs. These data are discussed briefly in the belief that they may lead to a clearer understanding of this aspect of the subject. Material and Experimental Procedure The material investigated was a cornmercial grade of S.A.E. 4140 steel, the composition of which was as follows: 0.37 per cent C, 0.77 per cent Mn, 0.98 per cent Cr and 0.21 per cent Mo. It was hot-rolled to a 1 1/8-in. round bar and normalized by air-cooling from 1800°F. (980°C.).

Jan 1, 1941

By R. J. Hafsten, E. S. Davenport, R. A. Grange

The influence of austenite grain size upon the hardenability of steel is now fairly well understood; for a given austenite, increasing the grain size increases the depth of hardening, and, since the latter is related to the fundamental transformation behavior of austenite, it follows that austenite decomposition must, in general, be retarded by increasing grain size. To date, very little quantitative information bearing directly on the effect of austenite grain size upon the progress and result of isothermal transformation has been published. Davenport and Bain,' and Zimmerman, Aborn and Bain2 have shown that the transformation is definitely relarded in hypereutectoid plain carbon steels at temperatures near and above the upper region of rapid transformation (Ar') when the austenite grains are increased in size. More recently, Griffiths. Pfeil and Allen3 investigated the effect of a series of different heating (austenitizing) temperatures upon the progress of isothermal transformation at 1245°F. (675°C.) and 745ºF. (395°C.) in a medium carbon, low-alloy steel; while they reported no measurements of the austenite grain size, their results suggest that increase in grain size retards austenite transformation at 1245ºF. (675°C), but has no appreciable effect at 745°F (395°C.). The present paper deals with the results of a study of the isothermal transformation of austenite in a single commercial alloy steel in which a fine-grained or a coarsegrained state was induced by appropriate selection of austenitizing temperature. The data are presented in the form of isothermal transformation diagrams, which clearly show that coarsening the grains lessens the rate of transformation of austenite to proeutectoid ferrite and pearlite—that is, at temperature levels above about 1000°F. (540°C.)—but is without significant effect at lower temperatures where the transformation product is bainite or martensite. It is to he presumed that the foregoing statement would be valid, at least in principle, for many other grades of steel; it confirms again that the mechanism of transformation to a pearlitic structure is fundamentally different from that to an acicular structure. A number of related observations were made, which seem to throw some light on the transformation process as it takes place in alloy steels, particularly at temperature levels in the vicinity of 1000ºF. (540°C.), where the transition from lamellar to acicular structures occurs. These data are discussed briefly in the belief that they may lead to a clearer understanding of this aspect of the subject. Material and Experimental Procedure The material investigated was a cornmercial grade of S.A.E. 4140 steel, the composition of which was as follows: 0.37 per cent C, 0.77 per cent Mn, 0.98 per cent Cr and 0.21 per cent Mo. It was hot-rolled to a 1 1/8-in. round bar and normalized by air-cooling from 1800°F. (980°C.).

Jan 1, 1941

By B. R. Queneau

Steel has been chosen as the metal whose solidification will be used to tie in the principles discussed in the previous papers. Although steel is the most important [ ] practical example that could be chosen, its solidification is complicated by the presence of many elements added either intentionally or present as impurities. The liquid steel bath in an open-hearth furnace contains carbon, manganese, phosphorus, sulphur, and many residual alloying elements such as nickel, copper, and molybdenum. The bath also contains oxygen, the concentration of which is a function of the carbon content, as shown in Fig. I. Deoxidizers such as silicon and aluminum may be added either before or after tapping depending on the grade of steel being made. There are four types of steel ingots: Killed, semikilled, capped, and rimmed, and these differ from each other in their state of oxidation. Each type of steel has advantages in the production of specific steel products, and it should be emphasized that no one type should be considered superior to the others. Fully deoxidized steels, known as killed steels, have little or no gas evolution on solidification. When the steel solidifies in the mold, shrinkage occurs which causes a large void known as "pipe." To minimize the amount of metal that has to be discarded on account of pipe, a big-end-up mold is used together with a refractory "hot top" which supplies molten steel to the main body of the ingot while solidification proceeds, Fig. 2. A section through a 32x32 in. ingot is shown in Fig. 3. The "hot top" volume is about 15 pct of the ingot, and the yield from killed steel in billet form is about 8o pct of the ingot weight. High quality machinery and tool steels are rolled from killed-steel ingots, but at the present time this represents less than 20 pct of the total steel production in the United States. In order to reduce cost and to increase

Jan 1, 1951

By C. E. Schwab

A lead-zinc orebody, in fairly strong quartzite and with a dip of 35" to 60°, is block-caved by use of scrams in a stair-step pattern up the ore footwall. Scram linings to handle coarse muck and permit the use of folding scrapers are developed by the use of end-grain wooden blocks to reduce maintenance and keep operating cost to a minimum. THE Bunker Hill mine, since its discovery in 1885, has steadily produced a high grade of lead-silver-zinc ore. By the end of 1952 over 21,000,000 tons of this high-grade ore had been produced by square-set mining, and reserves in the mine continue to be very satisfactory both as to quantity and grade. For many years prior to 1941, mine production and mill capacity had been 1200 tons of feed per day. Closely adjacent to the mill, and stored behind dikes, coarse jig tailings had been impounded during the time preceding the advent of fine grinding and selective flotation. When manpower became short in 1941 and sink-and-float preconcentration was proved successful, mill capacity was increased to 1800 tons per day to treat these jig tailings economically. By 1946, because the supply of jig tailings was limited, underground exploration was started to discover and prove ore reserves of low-grade material which could be mined by an appropriate bulk mining method. During the years of square-set mining many possible areas of low-grade mineralization had been observed. One chosen for the first exploration work was sufficiently remote from active mining areas so that subsidence, if an ore-body were proved, would cause no problem. Also, old adits and workings were still open and in good enough condition so that exploration in the mineralized zone could be started with a minimum of preparatory work. In 1948 an orebody was proved of sufficient tonnage, of a grade about 2 pct Zn, 0.5 oz Ag, and 1.0 pct Pb. It was decided to use block-caving, the only appropriate mining method by which this grade of ore could be economically recovered. Exploration for additional reserves in other areas of the mine is continuing, but ultimate results are not known at this time. With more sink-and-float capacity, larger ball mills, and more flotation machines, mill capacity was increased to 3000 tons per day, permitting the mining of ore in the square-set area at a maximum rate not usually achieved, because of the scarcity of labor. Increased mill capacity also permits block caving and the mining of jig tailings at variable rates to keep mill feed up to 3000 tons per day. Fortunately the three types of feed are amenable to the same mill circuit and reagents for recovery of Pb and Zn. For example, during the first 10 months of 1952 square sets produced 827 tons per day, block-caving 1421 tons per day, and jig tailings 643 tons per day, an average daily production of 2891 tons for all three products. Exploration had proved the existence of an ore-body 1000 ft long and 165 ft wide in horizontal section, see Fig. 1. Company engineers were concerned only with the vertical extension, about 300 ft, from an old level to the surface. Much of this almost outcropped, Fig. 2. The ore lies in the hanging wall of a major fault of the Bunker Hill mine, standing at 65" in one end of the zone and separated from the fault by a wedge of waste, see Fig. 3. This wedge pinches out near the center of the zone, at which point the ore dips 45", lying nearly on the fault, Fig. 4. The remaining portion lies on the fault and conforms to the fault dip of 35", Fig. 5. Open-pit mining for the top of the ore was considered, but since the ore zone dipped into and under the mountains, adverse waste-to-ore ratios precluded use of this method. The ore occurs in massive quartzite of sufficient strength to support untimbered drifts, crosscuts, and raises. Zones of weakness in the quartzite are bedding, jointing, and small faults or slips. The mineralization, which occurs as small stringers of sphalerite and galena as well as pyrite, creates another line of weakness. The mineral veins or veinlets in themselves are high-grade. Their size and regularity and the amount of barren quartzite by which they are separated determined the limits of mineable ore, which are all assay limits except for the one determined by the major fault. Block 1 Without any background of caving in this type of quartzite, engineers selected the first block on the very steep end of the zone. Compelling reasons prompted this decision. The steep portion of the ore in Block 1 was of the lowest grade, so that if difficulties were encountered no very valuable ore would be lost, while the experience gained might be applied in mining the remaining blocks. A block 200x200 ft was laid out, with four scrams spaced 50 ft apart for drawing and placed at a right angle to the strike. Finger raises were placed in a 25-ft interval grid pattern, with flat undercutting done by crosscuts at the undercut level 25 ft above

Jan 1, 1954

By G. P. Conard, E. H. Rennhack

The creep behavior of hot-rolled, hypoeutectic Zn-Ti alloys was investigated in the temperature range from 0.43 to 0.53 TM. Secondary flow was found to originate primarily from strain-induced gvain growth where grain boundary )nigvation served to relieve the strain energy of distortion introduced by slip, grain boundary sliding, and subgvain formation. The extent to which this recovery mechanism operated was determined by the ratio of grain width to the spacing between planar fibers of TiZn,, compound particles generated in these alloys during rolling. When this ratio was unity, creep resistance demonstrated a marked improvement. In this condition, which was fulfilled by annealing following rolling, structural stability was enhanced with decreasing grain size below the equicohesive temperature (-0.5Tm), while the reverse was true above this temperature. TITANIUM concentrations approaching the eutectic composition of 0.23 wt pctl have been shown to promote a significant increase in the creep resistance of rolled zinc,2 The alloying effect created with titanium is somewhat unique; a structure closely resembling that of a fiber-reinforced metal composite can be developed which selectively modifies creep strength in preference to other mechanical properties. In an earlier investigation,~ the present authors found that, while the fiber network, composed of individual TiZn,, compound particles, had a distinct influence on rolled texture, the crystallographic variations produced were of minor importance with respect to creep. Rather, creep resistance seemingly increased when the grain size appeared to coincide with the in-terfiber spacing. The work described here was undertaken to explore this effect in greater detail. EXPERIMENTAL PROCEDURE Three zinc-base alloys containing 0.05, 0.12, and 0.16 wt pct Ti were prepared from CP zinc and iodide titanium in the form of 4 by 2 by f in. chill-cast ingots. The melting and casting procedures for these alloys have been detailed el~ewhere.~ Individual ingots of each alloy were hot-rolled at 200°C (392°F) to total reductions of 10, 25, 50, 75, and 90 pct in from one to five passes, respectively, employing a 10-min reheat prior to each rolling pass. With grain, tensile-type creep specimens with a 1-in.-long, -in.-wide gage section were machined from the rolled strips for test purposes. Annealing studies to explore the influence of grain size on secondary creep flow were carried out at 400°C (752°F) in argon for times extending up to 60 min. The grain-size effect was evaluated in terms of average grain width and length values statistically derived from lineal intersection measurements.4 A similar method was applied in establishing the average interfiber spacing, i.e., average perpendicular distance between adjacent planar fibers. The creep characteristics of the alloys were investigated by means of constant-load and constant-stress creep tests. The former tests were conducted at 25°C (77°F) under an initial stress of 10,000 psi, while the latter were performed in the range from 25°C (77°F) to 90°C (194°F) at stress levels varying from 8000 to 22,000 psi. Total specimen strain, as determined with Budd HE-1161-B strain gages, was in excess of 0.10. Maintenance of constant stress was achieved through periodic load reductions made at 0.01 strain intervals to compensate for the attendant incremental reduction in specimen cross-sectional area. The maximum indicated error in the applied stress at these strain intervals was less than 3.0 pct. RESULTS AND DISCUSSION Constant-Load Creep. In an effort to clarify the in-terrelation between interfiber spacing and grain size with respect to the creep resistance of the Zn-Ti alloys, their separate effects on secondary creep rate were determined as a function of titanium content and rolling reduction. These results are set forth in Figs. 1 and 2, respectively. The average grain diameter plotted in Fig. 2 was resolved from average grain width and length values. No data are presented for reductions of less than 50 pct because of the inability to obtain consistent measurements on these strips. The curves of Fig. 1 indicated that, for a given titanium content, a decrease in interfiber spacing, as produced with increasing reduction, promoted a decrease in creep rate. Depending on titanium content, however, wide variations in creep rate occurred at the same interfiber spacing suggesting that interfiber spacing, by itself, has little or no influence on creep resistance. Grain size, on the other hand, decreased progressively with both increasing rolling reduction and titanium content, the effect of which led to a pronounced decrease in creep rate, particularly when the average grain diameter became smaller than 3.0 x 10"4 in., Fig. 2. The continuity of this relationship tended to support the view that grain size rather than interfiber spacing was predominant in controlling secondary creep. Annealing Effect. The observed dependence of creep flow on grain size suggested that a further contribution to creep resistance would result when the alloys were annealed to effect a coincidence between grain width and interfiber spacing, see Fig. 3(b). ~eiides creating an immediate barrier to grain boundary movement, annealing offered the possibility of providing increased structural stability by eliminating many high-energy, mobile grain boundaries.= To test this hypothesis, specimens from the Zn-0.16 Ti strips reduced 75 and

Jan 1, 1967

By A. N. Chirico

This paper reviews the three major distillation processes: multiple effect (LTV) evaporation, multi-stage flash distillation and vapor-compression forced circulation evaporation. Scale preventative measures are discussed for all saline water applications. Operational data is presented on the Freeport, Texas, demonstration plant, which is the first government facility to produce one million gallons per day of fresh water for a municipality. There has been much publicity concerning the water crisis that confronts many peoples today. There is little doubt that the arid regions - which include the Middle East, parts of Africa and the Caribbean — have suffered to no slight extent for the lack of this most precious commodity. But what about our own country? Government experts have extrapolated demands and flatly predict that by 1980 we will be faced with a shortage of 80 billion gal per day. The validity of this prediction has been disputed by others; however, it appears certain that there will always be a natural abundance in some areas, a shortage of supply in other areas. Distributing our total natural water resource equitably would be impossible. Transmission of water by means of aqueducts can be an expensive undertaking. The controversial Feather River Project in Calif. is an example. The estimated cost for this venture is a staggering three billion dollars. As our population continues to increase and our standard of living rises, agricultural and industrial requirements will be proportionate. What can be done to avoid a crisis? We can conserve and use our water for industrial and irrigation purposes more judiciously: we can attempt to eliminate pollution of our natural resources from sewage and industrial wastes; we can develop, while there is time, saline water conversion processes for the massive production of low cost fresh water. The scope of this paper will be limited to only the distillation type processes that are commercially feasible. The first step in making potable water is to find a source of raw material. An inexhaustible supply is provided by oceans in coastal regions, but the supply of water is more critical in the inland communities of our country. The source of raw material in these. regions is brackish well water and this must be utilized. There is a significant process difference when handling brackish water compared to seawater and this brings out an important fact: No single conversion method can be universally applied to solve all the water problems. Composition of the raw water and degree of distillate purity are factors which must be considered before a particular process is selected. Local conditions at the plant site, fuel costs, labor costs, disposal facilities, etc. are other equally important factors which must be evaluated. WATER CONVERSION PROCESSES Conversion processes commercially feasible today are: 1) multiple effect evaporation, 2) multiple flash distillation, 3) vapor compression distillation and 4) electrodialysis. The first three are distillation processes which take potable water out of the raw water, while the fourth is a membrane process which takes out the salt. In addition to the above there are a good number of other promising methods for production of potable water, many of them in the basic research stage. Freezing is another promising process with commercial potential. This process hinges upon the formation of ice crystals which are free of salt occulsions. Separation and washing of the crystals are problems that must be solved before this process can be considered commercially feasible. Freezing processes have several advantages mostly attributable to the low temperature of operation. This low temperature reduces the scaling and corrosion problems encountered in higher temperature operations. Several different freezing processes are being considered and will be tested in the pilot plant at Wrightsville Beach. One process is a flash freeze process, a second uses a secondary refrigerant such as butane for freezing, and a third process employs a secondary refrigerant particularly controlled to produce large ice crystals. Of the above processes, only the distillation processes are reliable when water of high purity is re-

Jan 1, 1963