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By E. C. Houston

The presence in the Tennessee Valley of extensive deposits of olivine, a silicate of magnesium and iron that contains approximatcly 28 per cent magnesium, has been recognized since 1896 when Lewis8 published a survey of basic magnesium rocks of western North Carolina. A recent field survey by T.V.A.7 showed that more than two hundred million tons of high-grade olivine occurs above local drainage levels in western North Carolina and northern Georgia. Except for sporadic attempts to work the olivine for its nickel and chromium contents,10 the ore received little attention industrially until 1926 when Goldschmidt3 suggested its use in the manufacture of refractories. Only one instance is recorded of an attempt to utilize the ore commercially for its magnesium content;11 in this case a process was used in which olivine was treated with sulphuric acid, the resultant mixture was leached with water, and the leach solution was purified and evaporated to form epsom salts, which was the end product. As a part of its program of contributing to the development of the natural resources of the region, the Tennessee Valley Authority became interested in the olivine deposits as a source of metallic magnesium because of their high magnesium content and proximity to hydroelectric power. Studies were undertaken to determine the feasibility of producing magnesium chloride by extraction of olivine. The experimental work was carried out successively at the T.V.A. Minerals Testing Laboratory, Norris, Tenn., at the Georgia State Engineering Station,* Atlanta, Ga., and at the T.V.A. laboratory at Wilson Dam, Ala. The present paper describes a process, developed through the pilot-plant stage, whereby magnesium chloride suitable for reduction to metallic magnesium can be prepared from olivine by extraction with hydrochloric acid and subsequent purification. Research on the magnesium-from-olivine process, originally intended for peacetime use, was given impetus by the shortage of magnesium that existed at the beginning of the current world war. By the time the process was sufficiently developed to justify a proposal for its inclusion in the war program, the shortage had been met by expansion and development of other processes. However, it is believed that the magnesium-from-olivine process may have advantages that will warrant consideration of its use after the war, when the. economics of the various processes rather than production on a wartime scale will be the criterion for commercial production of magnesium. Description of Process Metallic magnesium is produced electro-lytically by the Dow and the Elektron

Jan 1, 1948

By P. G. Dunn

Geologic studies during development at Copper Flat were directed at acquiring the necessary information in evaluating a low-grade porphyry copper deposit. In addition to the geologic mapping and core-logging of a typical exploration project, these studies included: - careful checks on the sampling and assaying, - selection of representative samples used to establish the recoverable amounts of precious metals in the ore, - examination of underground workings driven to provide samples both for metallurgical testing and for assay comparison, - evaluation of plant site and waste dump areas as non-material, including a placer examination of the tailings disposal area, and location of an adequate water supply. All these investigation were carefully documented to provide the necessary data both for the engineering design and, more importantly, for the feasibility studies required for successfully financing the project.

Jan 1, 1985

A filled stope is one in which the support for walls and men and, at times, for the back of ore, is furnished by waste rock or sand tailings. The filling may be rock sorted out in the stope or from the walls, develop-ent, or the surface. The orebody is mined in sections, each practically an open or timbered stope, filled wholly or in part before adjacent ground is attacked. As a rule, the filled-stope method is limited to overhand flat-back, stepped-face, or rill stopes. The examples given are Copper Range, Iron Cap, Verde district, Zaruma district, Lucky Tiger, and Silver King Coalition.

Jan 1, 1925

By James V. Thompson

SINCE it was introduced in 1943 to recover chromite from Oregon beach sands, the Humphreys spiral concentrator has proved successful in several fields of wet mineral beneficiation. By the end of 1957, 9390 Humphreys spirals had been manufactured. Most of these are still in service. The spiral does not offer a panacea for all mineral dressing problems. Its proper application can best be determined by test work. Spirals present a unique advantage for the metallurgist to make tests in a full-size machine rather than a miniature model, without the risk involved in scaling up results. With only 10 to 40 lb of sample, the operator of a closed circuit test unit employing a full-size Humphreys spiral can conduct preliminary tests with full-scale loadings of 0.5 to 2.5 tph. With larger samples, from 300 to 500 lb, he can run longer multi-stage tests to obtain reliable data for the next step-pilot plant design. The manufacturer of the Humphreys spiral concentrator maintains a fully equipped ore dressing laboratory and by insisting on test work prior to sales has largely prevented misapplication of the spiral.

Jan 1, 1958

By Robert B. Sosman

The chance that a Howe Memorial Lecturer will be able to refer back to a personal contact with the distinguished metallurgist for whom this lectureship is named grows steadily I I did not have the pleasure of his personal acquaintance, but I did receive from him in 1916, quite unexpectedly, a letter commenting On a paper that I had recently published27 On "Types of Prismatic Structure in Igneous Rocks." The paper was written for geologists and petrologists, but it had an application, naturally, to the crystallization of iron and steel in a mold. The letter impressed me at the time, and still does, with the breadth of of Howe's interests and his perseverance in keeping up with the progress of any branch of knowledge that had metallurgical connotations. Scope of the Lecture During several years preceding the date mentioned I had worked in collaboration with Arthur L. Day and E. T. Allen8 at the Geophysical Laboratory, Carnegie Institution of Washington, on the temperature scale as defined by the nitrogen thermometer at high temperatures. Later (1928-1947) I had the opportunity of helping to apply this experience to the pyro-metric problems of the steel industry. Because of the range of its temperatures, the multiplicity of the methods used, and the variety of its purposes, pyrometry in the open-hearth process has always offered a fertile field for both research and development. I am therefore devoting an hour to the subject of temperatures in the basic open-hearth furnace, the furnace that makes most of our steel in the united States. I would direct your attention particularly to the choice of the first two words in the title of the Lecture. One sometimes hears or reads of the ((temperature of such-and-such a furnace," as if it were a single, measurable, characteristic quantity. I need hardly emphasize to any one who has ever operated a furnace or a kiln that " temperature of the furnace " is a meaningless phrase. Even if we confine our attention to the space enclosed by the roof, walls, and hearth of an open-hearth furnace, it is doubtful whether any such space has ever been so uniform in temperature that the phrase would have a meaning. In any furnace, there are many different temperatures, capable of being measured at many different places, and actually being measured for several different purposes. These pyrometric purposes, methods, and results, if given in detail, would expand this lecture into a book on the basic open-hearth process. I must therefore confine myself to a statement of the range of temperatures as they have been observed in various parts of the furnace, indicating in a general way why they are measured, and mentioning the methods that are available without attempting to describe these

Jan 1, 1949

By Robert B. Sosman

The chance that a Howe Memorial Lecturer will be able to refer back to a personal contact with the distinguished metallurgist for whom this lectureship is named grows steadily I I did not have the pleasure of his personal acquaintance, but I did receive from him in 1916, quite unexpectedly, a letter commenting On a paper that I had recently published27 On "Types of Prismatic Structure in Igneous Rocks." The paper was written for geologists and petrologists, but it had an application, naturally, to the crystallization of iron and steel in a mold. The letter impressed me at the time, and still does, with the breadth of of Howe's interests and his perseverance in keeping up with the progress of any branch of knowledge that had metallurgical connotations. Scope of the Lecture During several years preceding the date mentioned I had worked in collaboration with Arthur L. Day and E. T. Allen8 at the Geophysical Laboratory, Carnegie Institution of Washington, on the temperature scale as defined by the nitrogen thermometer at high temperatures. Later (1928-1947) I had the opportunity of helping to apply this experience to the pyro-metric problems of the steel industry. Because of the range of its temperatures, the multiplicity of the methods used, and the variety of its purposes, pyrometry in the open-hearth process has always offered a fertile field for both research and development. I am therefore devoting an hour to the subject of temperatures in the basic open-hearth furnace, the furnace that makes most of our steel in the united States. I would direct your attention particularly to the choice of the first two words in the title of the Lecture. One sometimes hears or reads of the ((temperature of such-and-such a furnace," as if it were a single, measurable, characteristic quantity. I need hardly emphasize to any one who has ever operated a furnace or a kiln that " temperature of the furnace " is a meaningless phrase. Even if we confine our attention to the space enclosed by the roof, walls, and hearth of an open-hearth furnace, it is doubtful whether any such space has ever been so uniform in temperature that the phrase would have a meaning. In any furnace, there are many different temperatures, capable of being measured at many different places, and actually being measured for several different purposes. These pyrometric purposes, methods, and results, if given in detail, would expand this lecture into a book on the basic open-hearth process. I must therefore confine myself to a statement of the range of temperatures as they have been observed in various parts of the furnace, indicating in a general way why they are measured, and mentioning the methods that are available without attempting to describe these

Jan 1, 1949

By J. B. Austin

In considering so complex a process as the smelting of iron in the blast furnace, there is obviously no single method of calculating efficiency that gives a complete appraisal of the performance of the furnace in all its several functions; such a comprehensive view as is required to evaluate producing ability and manufacturing costs for a given furnace is obtained only by considering a group of efficiencies, each of which measures the performance of the furnace from a specific point of view. For instance, there is the rate of consumption of coke per ton of iron produced, which is probably the most frequently considered, and is certainly one of the most important of the group; there is the efficiency of recovery of iron charged; and there is the efficiency of utilization of energy, both chemical and thermal, in some respects related to the former two yet in other ways independent of either. In each of these cases, the calculation can be made on the basis of the actual input of material or energy, or it may be based upon a comparison with the minimum amount of material or energy that would be required by a "perfect" furnace; that is, an imaginary ideal furnace analogous to the perfect steam engine used in thermodynamic calculations, when this furnace is operating under optimum conditions. Moreover, the furnace itself can be considered either as an apparatus for smelting iron or, taking a somewhat less common point of view, as a gas producer yielding iron and slag as by-products. Some of these efficiencies are more useful than others, yet all are instructive; for a knowledge of them not only leads to good engineering practice from the standpoint of control but also discloses limits to possible improvement in performance and indicates the lines along which improvement is most likely to be profitable. Estimates of some of these efficiencies have appeared from time to time in the literature, but many of them are open to objection because they are based on data of uncertain accuracy or because they have been caleulated without due regard to the thermodynamic principles involved. Moreover, so far as the author is aware. no general survey of the blast furnace comparing its performance in all the aspects mentioned has been made.

Jan 1, 1938

By J. B. Austin

In considering so complex a process as the smelting of iron in the blast furnace, there is obviously no single method of calculating efficiency that gives a complete appraisal of the performance of the furnace in all its several functions; such a comprehensive view as is required to evaluate producing ability and manufacturing costs for a given furnace is obtained only by considering a group of efficiencies, each of which measures the performance of the furnace from a specific point of view. For instance, there is the rate of consumption of coke per ton of iron produced, which is probably the most frequently considered, and is certainly one of the most important of the group; there is the efficiency of recovery of iron charged; and there is the efficiency of utilization of energy, both chemical and thermal, in some respects related to the former two yet in other ways independent of either. In each of these cases, the calculation can be made on the basis of the actual input of material or energy, or it may be based upon a comparison with the minimum amount of material or energy that would be required by a "perfect" furnace; that is, an imaginary ideal furnace analogous to the perfect steam engine used in thermodynamic calculations, when this furnace is operating under optimum conditions. Moreover, the furnace itself can be considered either as an apparatus for smelting iron or, taking a somewhat less common point of view, as a gas producer yielding iron and slag as by-products. Some of these efficiencies are more useful than others, yet all are instructive; for a knowledge of them not only leads to good engineering practice from the standpoint of control but also discloses limits to possible improvement in performance and indicates the lines along which improvement is most likely to be profitable. Estimates of some of these efficiencies have appeared from time to time in the literature, but many of them are open to objection because they are based on data of uncertain accuracy or because they have been caleulated without due regard to the thermodynamic principles involved. Moreover, so far as the author is aware. no general survey of the blast furnace comparing its performance in all the aspects mentioned has been made.

Jan 1, 1938

By S. J. Aresco, George E. Keller, J. Visman

INTRODUCTION The accurate sampling of coal, as with most minerals, is a difficult task. Coal is a very heterogeneous material made up of different types of coal and varying amounts of mineral matter. The product as mined may contain all of the layers of coal and impurities found in the seam as well as portions of the strata above and below the coal seam. The preparation plant is the device to size, crush and/or remove impurities so that the coal may be shipped as a saleable product. Sampling may be needed at many stages in the preparation process. Although this chapter is mainly concerned with sampling in connection with preparation processes, the principles will apply to all coal sampling. The main reasons for sampling in connection with coal preparation are: 1. To determine the washability characteristics of the raw coal by means of float and sink tests. These may be used for the design of a preparation plant, prediction of results to be obtained or for monitoring raw coal delivered to the plant. 2. To check the performance of various operating units in the plant, either by float and sink tests or chemical analyses. 3. To determine the analytical characteristics of the products produced, such as moisture, ash, Btu, sulfur, etc. HISTORY The earliest accepted methods of sampling coal in the United States were given in U. S. Bureau of Mines publications by J. A. Holmes,1 G. S. Pope2 and A. C. Fieldner.3 The American Society for Testing and Materials more or less adopted the methods proposed by the U.S. Bureau of Mines in their Standard D-21-1916, and it remained a standard for many years. Briefly, the standard called for a 500 pound sample for coals less than. 3/4 -in. in size and a 1,000 pound sample for all coals over ?4 -in. in size. No mention was made of increments but there was an instruction that the sample should spread over the coal to be sampled. Sample preparation was by hand crushing with the alternate shovel method for reduction to 250 pounds followed by coning and quartering below 250 pounds. Obviously, with the amount of work involved, this method of sample preparation was rarely followed. This method of preparation resulted in samples that were practically air dried because of long exposure while crushing, shoveling and quartering. In the late nineteen twenties and early nineteen thirties, studies for more practical methods were begun. Dr. E. S. Grummell4, Imperial Chemical Industries, Ltd, London, summarized the work to date at the

Jan 1, 1968

By G. Horvay, J. G. Henzel

Nomograms and charts are provided which permit rapid determination of the mold-casting interFace temperature and the speed of solidification when a semiinfinite ingot is cast into a semiinfinite mold. The physical properties of the mold, the frozen metal, and the liquid metal are not assumed to be equal, but they are assumed to be temperature independent. The results are correlated with charts prepared by Paschkis and Hlinka—using Columbia University's Analog Computer—for the freezing of finite ingot slabs when a constant surface temperature is impressed, and with experimental cooling curves obtained by Pellini in sand and iron molds for 7 in.-sq steel castings. x = coordinate directed to right of zero (freezing direction) y = coordinate directed to left of zero (melting direction) e = position of freezing front (in x direction) ? = position of melting front (in y direction) $ = temperature (function of position and time) ? = fixed temperature 2L = width of finite slab Y = a fixed position in the semiinfinite mold, or the width of a finite mold (see Section 7) Properties y = density, lb per cu ft c = specific heat, Btu per lb deg F k = conductivity, Btu per ft hr deg F X = heat of fusion, Btu per lb k = k/Yc = temperature diffusivity, sq ft per hr* b - = = - heat diffusivity, Btu per sq ft deg F Vhr Subscripts 2 = pertaining to the still-liquid metal (case of freezing), or the medium which furnishes the heat (case of melting) 1 = pertaining to solidified metal (case of freezing), or to molten metal (case of melting)* 0 = pertaining to mold (case of freezing), or to the still-solid metal (case of melting) f = pertaining to fusion condition (eg.,?f - fusion temperature) i = pertaining to the location x = 0 (the mold-ingot "interface")

Jan 1, 1960

By Paul H. Hunt

MANY MISUNDERSTANDINGS have arisen regarding -Al the purchase by the Government of 24,000,000 oz. of domestically produced silver annually for the next four years at a price of 64 1/2c. to the producer. Some editorials have an¬nounced rather sarcastically that be¬cause of the strong western silver bloc in Congress, the Administration is paying a bonus of approximately $22,000,000 to a few large silver produc¬ers of the West, the amount being figured on the total purchase of about 100,000,000 oz. and the difference between the Government price and the world price for silver. Actually the Government will make a profit on this purchase, due to seigniorage, of something over $60,000,000. The 96,000,000 oz. of silver, for which the producers will receive approximately $62,000,000, will be produced in association with at least $100,000,000 worth of lead, zinc, copper and gold; the greater part of this $162,000,000 worth of metal will be produced at little profit to the mining companies, as will be shown later, because of the low prices for lead, copper and zinc. This amount of money will be spent largely for labor and supplies, thus greatly relieving the national burden of unemployment. Certainly, western mining, in the purchase of this silver, is not victimizing the Federal Government.

Jan 1, 1934

By H. S. Greismer

Alabama washes a larger percentage of its total coal output than any state in the Union. For producing coking coal, three-compartment jigs are favored; mines providing, steam and commercial coal use single-compartment jigs exclusively. Chemists are as necessary to washing plants as recording gages are to power plants. Experiments in Alabama indicate that the sludge released by coal-washing plants can be deposited in streams and on agricultural lands without disastrous results. CAMPBELL, 1 in 1896 said: "The Birmingham district in Alabama has certain great advantages for there are few places in the world where fuel and ore are so near together, although, unfortunately, both are of inferior quality; the ore being low in iron and high in phosphorus and the coal giving a weak and impure coke." This statement could not have been, questioned in 1894, but by 1896 several Robinson-Ramsay washers had been put into operation and weak and impure coke was a thing of the past. The Warrior coal field of Alabama contains six seams that yield coking coal of excellent quality. In descending- order, they are Brookwood, Milldale, Pratt, America, Mary Lee, and Black Creek. In each of these, however, bands of rock and bone coal of varying thickness are stratified with the coal; and while some of these impurities can be separated from the coal by the miner, much of it must be loaded out with the coal: Consequently, unless the coal is washed before being coked, it will yield a coke of varying ash and sulfur content quite unsatisfactory, for blast-furnace use. At present, the Gulf States Steel Co. is producing run-of-mine coal at its Virginia mine, from the America seam, that is uniformly low enough in ash to permit of coking without washing, but this is the only exception to the above statement. Alabama was the first state to experiment seriously with coal washers, was the first to install washers on a large scale and, up to the present, has maintained the lead. The Alabama State Mine Inspector reports that during 1923 20,919,303 tons of bituminous coal were mined in Alabama; 12,858,499 tons of which were delivered to coal washers for treatment.

Jan 9, 1924

By Gerhard Derge

THE extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: I. The reaction C + FeO -+ Fe + CO is rapid enough to make the correct sampling of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautio1 and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to A1203, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. 2. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. INDIRECT METHODS Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed more readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached, is not , well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the reactants than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equilibrium relations may be used more readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory means of determining oxygen for the calibration is felt keenly. For example, the statistical analysis of the relation between carbon and oxygen4 5 illustrates that even in a single plant wide variations exist under normal conditions of operation. Nevertheless, this is one of the best methods now

Jan 1, 1943

By Donald Barton

Geophysical methods of prospecting taken as a whole do not seem to offer much promise to a young man planning to enter them in the future. They have come to stay, to be sure, and they will continue in at least moderate use for a long time. Domestic use of those methods presumably is at a maximum at the present time. Geophysical pros-pecting is expensive; the effects of the law of diminishing returns in efficiency in finding prospects can already, be recognized. Small oil companies, independent oil operators, and royalty buyers have been doing much geophysical work. But in face of the increasing costs of discovery of prospects and in face of the probably decreasing favorability of the prospects discovered, I expect to see a sharp drop in their use of geo-physics within the next 10 years. The major oil companies and the larger small oil companies will continue to use geophysics indefinitely, but it seems doubtful whether the very extensive domestic campaigns of a few companies will be maintained for many years, certainly not for 10 years. The use of the geophysical methods in foreign countries has not yet reached its peak, and probaby will continue to increase for several years. That peak level of activity will probably be held for 10 years, although the site of maximum activity will shift from country to country; by the end of 25 years from now, I should expect the foreign use of the methods to have leveled off to one-fourth to one-half the peak level. Foreign service in geophysics does not seem to offer an attractive career, except for men of exceptional disposition. Young men just out of college, who are willing and who can afford to spend three or four years having a fling at adventure before settling down, will find it attractive, but when their tour of foreign service is over, they probably will have harder work finding a job than when they were seniors, and their foreign experience will count for little, except for further foreign service. A few men, mainly the higher men, will have headquarters at civilized or semi-civilized cities and towns or at permanent oil-company towns, and can

Jan 1, 1938

By Bruno V. Nordberg

The high cost of coal in Butte and the development of large amounts of cheap electric power from the Missouri river caused the Anaconda Copper Mining Co. in 1908 to make an investigation as to the possibility of adapt- ing this cheap electric power for the operation of their many large hoisting plants. At this time electric power had already been adopted for practically all other power purposes around the mines, such as pumping, compressing air, etc. The map (Fig. 1) shows the location of the mines of the Butte mining district. These mines are located within a circle of approximately a 1-mile

Jan 1, 1914

By C. J. Bier, J. F. O?Keefe

THIS study was carried out with copper because it represents the simplest form of sintering, in that but one metal is involved and all reactions occur in the solid state. [ ] The present work will cover three variables affecting the sintering process; namely, briquetting pressure, sintering temperature and time in hot zone. Although strength and dimensional changes were observed, this is primarily a metallographic study of the sintering process in copper. The term "sintering" should be understood to mean the process by which the metal powder particles of the compact become united into one body. MATERIAL USED The copper powder used was made from reduced copper oxide, and is typical of a grade used for the mass production of parts formed of metal powders. The screen analysis of the powder was as follows: [ ] The minus 325-mesh analysis was made by using a Roller Air Analyzer.1,2 The apparent density is here defined as the weight per cubic centimeter of the [ ] loose, unpacked powder as measured with the Hall flowmeter. The value for the powder used was 2.57 grams per cubic centimeter.

Jan 1, 1944

By J. M. Tobin, L. H. Cadoff, L. M. Adelsberg

The reaction between liquid zirconium and graphite at temperatures above 2000 °C has been investigated. The reaction products were found to be carbon-saturated zirconium metal and ZrC which formed between the graphite and the metal. Parabolic growth behavior was observed for the ZrC Phase at all temperatures of this investigation. The parabolic growth constant at temperatures between 2000° and 2860°C was measured to be 1.83 exp 84,300/RT) sq cm per sec. The reaclion mechanism was proposed to be the rapid carbon saturation of the liquid metal and the formation of ZrC at the metal-carbide interface with diffusion of carbon through the ZrC, the "rate - determining step" of the reaction. The concentration-independent diffusion coefficient of carbon in ZrC, (DZrC), was expressed as 0.95 exp? 78,700/RT) sq cm per sec. This value mas calculated using the temperature-invariant ZrC phase fields proposed in the literature. The [ZrQiq)] — [ZYQiq) + ZrC] phase boundary over the temperature range 2000° to 2800°C was determined and the ZrC + C eutectic temperature was found to be 2890° ± 50°C. ThE Group IV and VB transition-metal refractory carbides are of interest because of their high melting points, high temperature strength properties, and relative inertness in certain corrosive environments. The present-day understanding of these materials, however, is limited by the general unavailability of accurate and reliable physical and chemical property data. This is due primarily to the difficulties associated with the preparation of suitable, high-density, high-purity carbide samples, and the achievement and control of uniform high-temperature environments. Accurate measurement of temperature is also an important factor limiting the reliability of reported data. The Zr-C reaction was selected for investigation because of the high melting point (>34000C) and favorable nuclear properties of the reaction product, ZrC. The direct reaction method afforded an opportunity to obtain kinetic data on the fully dense carbide. In this paper, layer-growth techniques were used to estimate the diffusivity of carbon in ZrC and to investigate the phase equilibria in the Zr-C system at temperatures above 2000°C. EXPERIMENTAL PROCEDURES AND DATA Crystal bar zirconium (99.9 pct Zr), purchased from the Nuclear Materials and Engineering Corp., and ZTA graphite (99.9+ pct) were used in this study. The analyses of the materials are listed in Table I. A schematic of the high-temperature carburization apparatus is shown in Fig. 1. The sample was a zirconium metal charge in a 1/2 -in.-ID graphite crucible which was capped with a tightly fitting graphite stern. The crucible and stem were designed to closely approximate black-body conditions. The graphite crucible was packed in lampblack (outgassed 1 hr at 2100°C) which provided insulation and thermal stability to the system. The inert atmosphere was maintained by a constant flow of high-purity argon or helium gas. The nozzle-diffuser section on the top flange was sufficient to prevent back-diffusion of air into the system. Chemical analysis of the carburized samples revealed oxygen and nitrogen concentrations of less than 44 and 20 ppm, respectively. The sample was heated by induction with a Westing-house 5 kw-450 kc power source. Temperature was measured with a Milletron two-color pyrometer which was sighted into the crucible by reflection from an overhead front surface mirror. Optical losses due to glass absorption and light reflection at air-glass interfaces were minimized by the employment of the dynamic-gas seal. It was found that no correction was required for the front surface reflector. The pyrometer was calibrated periodically against a U.S. Bureau of Standards tungsten ribbon secondary standard. Temperatures inside the crucible were also calibrated against the Zr-ZrC eutectic (1850°C)1 and the Nb-Nb2C eutectic (2335°C)2,3 temperatures and agreed to within ±10°C of these values. The temperature was controlled by manually adjusting the power input; variations of

Jan 1, 1967

By R. E. Reed-Hill, W. H. Hartt

The "(3034) " twin lamellae in magnesium have been reexamined using electron microscope replicas. The double twinning sequence (1011)- (1012) for these lamellae has been reconfirmed. Evidence is presented showing that the irrational habit of these twins is probably the direct result of a need to accommodate the second-order twinning shear. This accommodation vesults in both an external shear in the matrix and an internal shear in the lamella. A model is presented which accounts for the experimental obseruations. HCP metals are generally characterized by strong textures in which the basal planes of the grains tend to be aligned parallel to the rolling direction in sheet or plate and to the axis of wires and rods. Since these directions are normally those in which finished products may be subjected to uniaxial tensile stress, these textures effectively place the crystals of magnesium objects in orientations unfavorable to both basal slip and {1012) twinning, the easily activated deformation systems of this metal. However, when magnesium crystals are deformed near room temperature by a tensile stress nearly parallel to the basal plane, another mode of deformation can occur.',2 This is _a double twin which forms first by twinning on {loll), followed by retwinning on (1012). The resulting twin lamellae are of considerable interest. First, they can be responsible for "brittle fracture''; when a tensile stress axis lies in the basal plane, because the reoriented crystal structure of a lamella is well-aligned for slip while the parent crystal is not. Extensive internal deformation may thus occur while the matrix is still almost undeformed. This deformation can produce a ductile rupture running the length of the twin.3 Complete failure of the specimen may then oc-cure by the spreading of cracks from one twin lamella to another, or by the movement of a crack into a grain boundary and then along grain boundaries. Since the the volume fraction of these doubly twinned elements is normally very small, the fracture may be classed as brittle, although the fracture mechanism is, of itself, essentially ductile. It is quite probable that the ductility transition, normally observed4 in magnesium at or slightly Obove room temperature, is closely associated with these second-order twins. The detailed relationship of these twins to fracture in single crystals will be the topic of another paper. The present paper is concerned with a second important aspect: the irrational habit of these double twins that falls close to {3034), or approximately 7 deg away from the primary (10il) twin habit. There is good reason to believe that this habit results directly

Jan 1, 1968

By F. Twyman, D. M. Smith

Those chemists (they are still greatly in the minority) who use the spectroscope, use it very often, and find it almost indispensable. As a means of detecting minute quantities of the metals it is unrivalled. A metal can be readily distinguished in the presence of any other element, compound, or mixture without the necessity of separation. The qualitative analysis of the metallic constituents of a substance, which the spectroscope gives so easily, is a sure basis for planning a chemical analysis. As the determination of each element proceeds the purity of precipitates may be checked as often as desired. If, possessing these advantages, the spectroscope has been neglected in general chemistry, it is not surprising that it was neglected in metallurgical chemistry; for many of the impurities which are of industrial interest, even when they are present in a metal or alloy in small quantities, are not then always easily detected by the examination of their visible spectrum. The history of the development of the art has been given in Bureau of Standards 19cientific Paper No. 444. The Development of Analysis by Spectrogbaphy Fig. 1 shows, by means of photographs taken with a quartz spectro-graph, what a valuable region of the spectrum is excluded if one has a visual instrument only. Wave length 4023 is about the end of the visible spectrum, the region from 3800 to 1854 being invisible. It is easy to understand then how it is that the vigorous resuscitation of spectrum analysis which has commenced in the last few years has been associated with the use of the quartz spectrograph; notwithstanding that the most useful instrument for the general inorganic chemist to have at his elbow, after the balance, is a good visual spectrometer.(1) 1 The revival of spectrum analysis is to be attributed chiefly to the work of W. N. Hartley with his co-workers, and to A. de Gramont. Hartley,

By K. H. Ribe

Water often enters an oil reservoir during completion or workover operations on a well and forms a partial "water block" to oil production. A mathematical study of radial two-phase flow, neglecting capillary effects, has been employed to study the formation of such a water block and subsequent re-moval by production from the well. The effects of reduced oil permeability about the well on the well productivity were studied. The fluid saturation distributions about the well during formation and removal of the water block have also been computed. Several relative permeability relations and viscosity ratios were employed. If water has invaded the formation, its influence through relative permeability effects alone can cause the following. 1. Oil productivity will be depressed for extended periods after production is resumed and will build up only gradually as the water is removed. 2. Oil injected for treatment of water blocking will delay rather than promote restoration of full well productivity by enlarging the region invaded by water. Thus, unless the specific action of chemicals contained in the oil is needed, oil injection appears undesirable. INTRODUCTION During oilwell workover operations, water may enter the oil-bearing formation from the wellbore. When production is resumed, oil must flow through the region invaded by this water. The presence of this region can cause both well productivity and oil production rate to be low and oil to be produced with high water-oil ratio for some time after production is initiated. This situation is sometimes described as a water block. The introduction of water into the formation may result in other actions which also lead to reduction in well productivity and which are also usually included in the connotation of the broad term, water block. Often considered, for example, are the possibilities of clay swelling by contact with fresh water and the formation of emulsions with the formation oil. If it is suspected that such specific actions have taken place, remedial treatments are undertaken which usually involve the injection of chemicals in oil. Since the introduction of water, even in the absence of specific interactions with the formation or oil, will cause a temporary water block (which might be misinterpreted as evidence of a more severe situation), it is of importance to evaluate the magnitude and duration of this blocking which results purely from the reduction in relative permeability to oil in the vicinity of the wellbore. It is also of interest to evaluate the effect of oil injection on the productivity of a well blocked by water in this manner. Inasmuch as this unfavorable condition may persist for some time, it may lead to premature condemnation of a workover or premature abandonment of a potentially productive pay zone. A quantitative evaluation of the influence of water entry on the oil productivity through changes in relative permeability was made by solving a radial form of the Buckley-Leverett equation. The distribution of water saturation around the wellbore during the entry of water was calculated and was followed by a similar calculation of the saturation distribution during the period of resuming production. At any stage in the removal of the invading water, knowledge of the distribution of its saturation permitted calculating the attendant loss in oil productivity. The influence of the shape of the relative permeability relationships was also evaluated by carrying out the calculations for two hypothetical cases. Further, the effect of the oil-water viscosity ratio was examined by repeating the calculations, for several ratios of unity and greater, with the same relative permeabilities. Fi-nally, results are presented to show how the length of time a well must be swabbed to resume production depends on the length of time it has been subjected to invasion by water. STATEMENT OF THEORY Differential Equations Water is assumed to enter a producing formation which is initially at the connate-water saturation and contains no gas. The water and oil are treated as in-