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By R. M. Treco

THE purpose of this work has been to investigate recrystallization characteristics of zirconium after cold working and annealing. In order to do this, hafnium-contain ing crystal bars of Foote Mineral Co. iodide zirconium were selected for high purity. maximum diameter (about ½ in.), brightness of surface, and absence of core wire. A typical lot analysis is shown in Table I. In order to obtain uniformity of starting material, all bars were cold-swaged to 0.310 in. diam, annealed for 2 hr at 1000°C, and furnace cooled.

Jan 1, 1957

By G. K. Manning, C. H. Lorig

TWO metallurgical tools have acquired wide use within the past several years as a means of studying the transformation characteristics of steel. One is a technique used first by Bain and Davenport for determining the transformation characteristics of a steel at constant temperature; the second is the end-quench hardenability test. Constant-temperature transformation curves like those of Bain and Davenport have done much to rationalize the metallography of steel; however, in commercial practices, constant-temperature transformation is seldom encountered, therefore only rarely can such curves be directly applied. The real reason for the determination of such curves lies in the fact that they provide a way of thinking about transformation that is both convenient and productive. The end-quench hardenability test is a more practical means of studying transformation, for, by correlating positions on the hardenability bar with shapes of different masses, an almost direct application of the results can be made. Unfortunately, the end-quench test, though practical, can do very little toward improving the metallurgists' way of thinking about transformation. These two metallurgical tools, dealing with precisely the same phenomenon, should be very closely associated in metallurgists' minds. Actually, they are frequently pushed into separate mental corners and considered as being more or less distinct and unrelated. The reason for this is that no strong connecting link between them has been developed. An attempt is sometimes made to relate these two tools by projecting the critical cooling rate on the isothermal transformation plot as illustrated in Fig. I. The critical cooling rate is considered as a constant rate-though in practical applications, cooling rates are never constant—and this constant cooling rate is given uniform significance from the Ae temperature down to the temperature of initial transformation. A little thought indicates the errors of such a procedure. Certainly the time interval spent just below point A of Fig. I cannot be as effective in promoting nucleation as is the time interval spent just above point B. Yet the procedure represented in Fig. I considers all the time spent between temperatures A and B to be just as effective in promoting nucleation as though all the time were spent at temperature B. Furthermore, change the shape of the isothermal curve between points B and C in any way desired, and the required critical cooling rate is not changed one iota. This cannot possibly be true. Such a way of thinking about critical cooling rates not only is incapable of giving any results that are quantitatively satisfactory but is likely to give very misleading qualitative results.

Jan 1, 1947

By G. K. Manning, C. H. Lorig

TWO metallurgical tools have acquired wide use within the past several years as a means of studying the transformation characteristics of steel. One is a technique used first by Bain and Davenport for determining the transformation characteristics of a steel at constant temperature; the second is the end-quench hardenability test. Constant-temperature transformation curves like those of Bain and Davenport have done much to rationalize the metallography of steel; however, in commercial practices, constant-temperature transformation is seldom encountered, therefore only rarely can such curves be directly applied. The real reason for the determination of such curves lies in the fact that they provide a way of thinking about transformation that is both convenient and productive. The end-quench hardenability test is a more practical means of studying transformation, for, by correlating positions on the hardenability bar with shapes of different masses, an almost direct application of the results can be made. Unfortunately, the end-quench test, though practical, can do very little toward improving the metallurgists' way of thinking about transformation. These two metallurgical tools, dealing with precisely the same phenomenon, should be very closely associated in metallurgists' minds. Actually, they are frequently pushed into separate mental corners and considered as being more or less distinct and unrelated. The reason for this is that no strong connecting link between them has been developed. An attempt is sometimes made to relate these two tools by projecting the critical cooling rate on the isothermal transformation plot as illustrated in Fig. I. The critical cooling rate is considered as a constant rate-though in practical applications, cooling rates are never constant—and this constant cooling rate is given uniform significance from the Ae temperature down to the temperature of initial transformation. A little thought indicates the errors of such a procedure. Certainly the time interval spent just below point A of Fig. I cannot be as effective in promoting nucleation as is the time interval spent just above point B. Yet the procedure represented in Fig. I considers all the time spent between temperatures A and B to be just as effective in promoting nucleation as though all the time were spent at temperature B. Furthermore, change the shape of the isothermal curve between points B and C in any way desired, and the required critical cooling rate is not changed one iota. This cannot possibly be true. Such a way of thinking about critical cooling rates not only is incapable of giving any results that are quantitatively satisfactory but is likely to give very misleading qualitative results.

Jan 1, 1947

By Arthur Winslow

Introductory.—The following paper is based upon a report on the lead- and zinc- deposits of Missouri, prepared for the State Geological Survey, which is now being printed. This report is the outcome of work prosecuted by the writer, assisted by Mr. J. D. Robertson, during the past five years. The studies in the State were supplemented by examinations of the similar ore deposits in Wisconsin and Arkan- sas. The report will contain in all about 800 pages, and the aim has been to make it complete and exhaustive, especially in descriptive matter. Naturally, only a brief outline can be presented here, and the reader is referred to the report itself for further details. Contents. I.—History and Statistics, . . 636 II.—Topography of the Region, . 639 III.—General Geology, . . .639 The Archean, . . .639 The Algonkian, . . 640 The Silurian, . . .640 The Devonian, . . 640 The Lower Carboniferous, 641 Tie Coal Measures, . 641 The Tertiary, . . .641 Structural Geology,. . 642 IV.—The Ore-Deposits, . . .643 Geologic Distribution, . 643 The Forms of the Ore-Bodies, . . .641 The Composition if the Ore-Bodies, . . .645 Gangues, . . . 645 Minerals, . . .618 Paragenesis of Minerals, . . . 651 The Structure of the Ore-Bodies, .... 651 V.—Descriptions of Types, . . 652 The Eagle Mines, . . 652 Shaft No. 23, . . 652 The Western Zinc Company or Oswego Lands, 651 The Gobar and Tomlinson Shaft, . 655 The Alba Company's Mine, 656 The Victor Mine, . . 658 The Bonne Terre Mines, . 660 General Geology, . 660 The Ore-Bodies, . 661 The Vallé Mines, . . 664 The Garatee Mines, . 664 The Corn-Stalk Diggings, . . .665 The Virginia Mine, . 666 The Conlogue Mine, . 667 VI.—The Mode of Formation of the Ore-Bodies, . . 670 The Formation of the Cavities. . . . 670 The Filling of the Cavities, . . . .675 The Formation of the Breccia Deposits, . . 673 The Formation of Circle Deposits, . . .674 The Impregnated Deposits of the Southeast, . 676 VII.—The Origin of the Metalliferous and Other Minerals, 676 1. Originally Deposited in Concentrated Condition, 676 2. Derived from Great Depths, . . .677 3. Original Diffusion, Supplemented by Lateral Secretion, . . . 678 4. Concentrated Through Surface Decomposition, 681

Jan 1, 1895

By B. L. Averbach, Morris Cohen, S. A. Kulin

The martensitic transformation can be initiated by elastic stresses at temperatures above M. in a steel containing 20 pct Ni and 0.5 pct C. Shear strains and normal tensile strains acting on a potential habit plane promote the transformation but compressive strains oppose it. THE strain sensitivity of the martensitic transformation has long been recognized. It is now well known that martensite formation can be induced by plastic deformation at temperatures below, and not too far above, the M, point.' However, the exact role of elastic vs. plastic strains and of the concomitant stresses has proved to be a very elusive matter. Many investigators2-' of the steel hardening reaction have made use of the stresses resulting from volume changes to account for such observations as the existence of retained austenite and its variation across the section of a bar, the change in the amount of retained austenite with quenching rate, and the self-stopping nature of the transformation when the cooling is stopped. The effect of applied strain as an independent variable has been studied in 70 pct Fe-30 pct Ni alloys by Scheil7 and McReynolds.8 Some data are also available for lithium and Li-Mg alloys,9 Cu-Zn,10 Cu-Sn and Cu-A1 alloys," and aus-tenitic stainless steels."-" It has been found that martensite formation can be induced isothermally, even at temperatures above M,, by mechanical deformation of the parent phase. The competitive nature of plastic yielding by slip and by the martensitic reaction has been depicted by Scheil.7 Basically, Scheil postulated that: 1—at temperatures not too far above M, (where austenite is less stable than martensite), a critical resolved shear stress (within the elastic range) is required to promote the transformation to martensite; 2—at and below M,, the austenite lattice becomes mechanically, as well as thermodynamically, unstable and shears over spontaneously into martensite without the application of external stress; and 3—at temperatures sufficiently far above M8, the critical resolved shear stress for martensite formation increases to a level above that required for slip, and plastic flow then supersedes the transformation when external stress is applied. Scheil's concepts were tested by McReyno1ds8 ho found no change in the elastic moduli (measured both statically and dynamically) of 71 pct Fe-29 pct Ni alloys in the vicinity of the M, temperature. Since the moduli did not approach zero or become negative on cooling to M,, it was concluded that the austenite lattice does not become mechanically unstable at M2, as postulated by Scheil. McReynolds also reported that M, is not raised by elastic stresses. Accordingly, plastic deformation was considered to stimulate the transformation by generating martensite nuclei in the distorted regions of the parent phase. The above issues with regard to the role of applied stress require clarification, if a basic understanding of the martensitic transformation is to be obtained. For example, in the reaction-path theory,'"," it is postulated that strain embryos exist in the austenite that provide part of the activation energy for the nucleation process. These embryos are visualized to be regions of localized strain in which the atoms in the austenite lattice are displaced part way along the path to their ultimate positions in the martensite. Consequently, it would

Jan 1, 1953

By G. R. Kotler, W. A. Tiller, H. V. Ashcom, S. O&apos, Hara, W. C. Johnston

The grain-refinement effect of electromagnetic stirring of Sn-Pb alloys during solidification is investigated at higher field strength and in larger-sized samples. It is found that the grain-refining effect is due to a crystal multiplication phenomenon rather than a nucleation phenomenon. The effect increases with sample size for a fixed field strength and a fixed supercooling bath temperatures. The effect in other alloys was investigated. IN a recent publication1 it was reported that significant grain refinement could be produced during the solidification of a supercooled melt of Sn-Pb alloy when a critical degree of electromagnetic stirring was present in the melt. Thus, for a particular supercooling, AT, a critical magnetic field, Hc, existed at which the number of grains per unit volume, n, increased rather abruptly by a factor of 103 to 104 as the field, H, was increased by a small amount. It was further found that the undercooling at which the melt spontaneously nucleated, ?Tn, was independent of the magnetic field. These authors matched their experimental results against the qualitative expectations of existing theories and found each theory somewhat unsatisfactory. One important question that was not answered in this previous work was "should the effect be classed as a nucleation phenomenon or as a crystal-multiplication phenomenon?" Other valid questions that need answering are: i) do higher magnetic field strengths alter the nature of the results?; ii) what is the effect of higher lead content in the alloy?; iii) what changes occur when one extends the experiments to larger-diameter samples?; and iv) is this a universal effect applicable to the grain refinement of all materials? The present work directs its attention to answering these five questions. The

Jan 1, 1965

By Martin Weinstein

A technique is described for preparing finegrained lead telluride by ultrasonic agitation of a solidifying melt. Material prepared by this technique is dense and chemically homogeneous. N-type PbTe, containing 0.03 mole pct PbIz, has been made and its thermoelecCric Properties have been measured as a function of temperature. For comparison, the properties of similarly doped PbTe made by cold pressing and sintering, and by extrusion, have also been measured. The ultrasonically prepared material compares favorably with the others in its thermoelectric-efficiency factor. Comparison of compressive-flow curves for the three kinds of PbTe show that the ulhasonically prepared material has much superior ductility. The cleavage strength of the ultrasonic material is related to the grain size, D, by the Petch relation:Extrapolation to infinite grain diameter yields a fracture strength of 5000 psi for single-crystal PbTe. WHEN metals and semiconductors solidify in a mold they normally assume one of three cast structures illustrated in Fig. 1.' Solidification in a casting starts at the mold walls where a large number of fine crystals of random orientation can be nucleated to form the chill zone. Because of the anisot-ropy of the growth rate, those crystals whose direction of maximum linear growth is parallel to that of the heat flow grow faster and crowd out the crystals of less favorable orientation. A second zone, having a preferred orientation, called the columnar zone, thus forms adjacent to the chill zone. The speed of growth of the columnar grains will depend, in the case of limited undercooling of the melt, on the rate at which heat can be abstracted. The columnar zone can extend to the center of the casting, Fig. l(a), but it is frequently followed, in solid-solution alloys, by another zone of equiaxed randomly oriented grains in the central portion of the casting, Fig. l(b). The equiaxed structure in Fig. l(c) represents the completely grain-refined case where the equiaxed grain size is small. The third type of structure is the most desirable because it imparts a somewhat higher strength for all except high-temperature applications, it reduces segregation of the doping constituent, and it reduces the possibility of hot tearing (the separation of grains due to the melting of a low-melting point constituent in the grain boundaries). In order to obtain fine-grained castings, the nu-cleation frequency must be increased and grain growth must be restricted. Various techniques have been employed for obtaining this end, namely: rapid cooling, vibration, and inoculation of the melt. The success of these techniques depends upon the characteristics of the metal species and on factors controlled by heat transfer through the crucible walls. Recent studies2" have shown that the application of ultrasonic energy to the solidifying ingot is an extremely powerful tool in the improvement of the crystalline structure of metallic castings. Both the mechanical properties and homogeneity of the ingots are improved. Ultrasonic oscillations may affect the crystallization process by 1) permitting subcritical nuclei to agglomerate and thus form nuclei of sufficient size to cause crystallization, 2) changing the state of surface adsorption of various catalysts found in the liquid melt, 3) breaking pieces of solid from the solidified surface near the supercooled region thereby increasing the number of possible nuclei, 4) causing temperature fluctuations to occur in certain parts of the melt thereby increasing the supercooling at specific points in the liquid, and 5) decreasing the critical nucleus size by increasing the pressure at specific points in the melt.' Various investigators have concluded that the effectiveness of the ultrasonic oscillations results from cavitation which disrupts the growing solid-liquid interface The present paper describes the application of ultrasonic oscillations to the crystallization of the semiconductor N-type PbTe. The purpose of this study is to prepare crystalline

Jan 1, 1964

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

THERE has been considerable discussion among A metallurgists and others interested in the development of titanium alloys as to the nature of the fine line markings which appear in the microstruc-tures of unalloyed titanium and a titanium alloys. These markings have been variously called x phase, etching pits, and twins. Figs. 1 to 3 show typical examples of the line markings as they appear, respectively, in high purity iodide titanium, commercial purity titanium rod, and a high purity a alloy containing 0.2 pct N. The commercial purity titanium sample, shown in Fig. 2, contains both line markings and some spheroidal retained-ß phase. The ß phase seen in this micrograph should not be confused with the line marking, since it originates from the iron present as an impurity in the sponge metal. It will be noted that the line markings seem to have a definite orientation pattern with respect to the grains and in titanium noticeably resemble the precipitation occurring in artificially aged high purity Al-Cu alloys. This similarity led to the hypothesis that the line markings observed in titanium and a titanium alloys resulted from precipitation of some unknown phase. With the work of Hägg1 and McQuillan2 as background, there was little reason to suspect hydrogen of being responsible for the line markings. Hagg reported that up to 33 atomic pct H was soluble in a titanium, and McQuillan reported an a solubility of up to 8 atomic pct. Furthermore, McQuillan examined metallographically a 5.1 atomic pct H alloy quenched from 300°C and stated that the structure appeared to be a single-phase a solid solution. Line markings have been observed frequently and were first noted by Jaffee and Campbell3 in 1949. They did not observe them in vacuum-annealed titanium and a Ti-O and Ti-N alloys, but did observe them in Ti-H alloys containing 0.25, 0.5, and 1 atomic pct H. They stated that it was doubtful that the markings were a second phase based on hydrogen, because 1 atomic pct was far from the accepted solid solubility of hydrogen in titanium. Finlay, Resketo, and Vordahl,4 in 1950, concluded that the markings were a true second phase as a result of observations on their etching characteristics. Anderson5 Commenting on these markings in titanium was inclined to associate them with hydrogen, but was loath to call them titanium hydride, because of the reported high solubility of hydrogen. Work at Battelle Memorial Institute for the Navy Bureau of Aeronautics," done concurrently with the work described in this paper, provided information on the experiment converse to that described by Jaffee and Campbell in 1949. This work showed that the amount of line markings in unalloyed titanium could be decreased by vacuum annealing at elevated temperature. It was suggested that this was the result of removal of hydrogen; previously, the data of Jaffee and Campbell9 howed that the markings appeared when hydrogen was added. Recent work at Battelle for the Ordnance Corps, Department of the Army, which is described here, now establishes the identity of the markings as a titanium hydride phase. A sample of high-purity titanium rod 1/4 in. diam, 0.009±0.001 wt pct H (0.43 atomic pct), Fig. 1, was resistance heated in a 0.05 micron vacuum for 41/2 hr at 1500°C. During the early states of heating, the pressure increased to 150 microns, indicating that gases were being evolved. After cooling in vacuum, the iodide titanium rod was analyzed for hydrogen. Vacuum-fusion analysis showed 0.0006 ±0.0003 wt pct H (0.03 atomic pct) to be present.* Metallographic examination of the vacuum-annealed rod showed only a transformed ß structure. There was no evidence of fine line markings, Fig. 4. A section of this vacuum-annealed rod was cold rolled to 0.040 in. thick sheet and annealed for 1 hr

Jan 1, 1953

By P. K. Koh, G. C. Dunn

Si-Fe single crystals in a number of selected orientations were cold rolled 70 pct and analyzed to obtain quantitative (110) pole figures. Stable end orientations were ddetermined, and the effect of orientation on deformation behavior was investigated. WHEN single crystals are cold rolled sufficiently, they rotate into end orientations that are stable or unchanged in position with additional deformation. The end orientations of heavily cold-rolled iron crystals, positioned in holes in copper to limit lateral flow and to simulate polycrystalline conditions during deformation, were determined by Barrett and Levenson.' They found that the sum of the end orientations, a pole figure for all the crystals studied, reproduced the essential features of the cold-rolled texture of polycrystalline iron. In. an investigation of Fe-Si alloys, Barrett, Ansel, and Mehl' observed little effect of silicon content on the textures of heavily cold-rolled samples. Since alloys with less than 4 pct Si are known to have the same slip systems as iron," it seems logical to expect that they would also have the same end orientations as those for iron. Whereas Barrett and Levenson in their study of single crystals were interested in the problem of the origin of the cold-rolled texture of polycrystalline iron, the present authors are more interested in the final cold-rolled textures of single crystals of Si-Fe from the point of view of their relationship to subsequent recrystallization phenomena which will be reported in another paper. Nevertheless, such points as the tendency of an end orientation not to rotate (stability), the tendency of a pole concentration to spread out, and the tendency of the crystal to widen during cold rolling become interesting separately when the initial orientations are selected already in end orientations. Also the initial orientations having a [I101 axis parallel with the transverse direction, which include the two end orientations (111) [Ti21 and (001) [110], comprise a series that needs further clarification regarding the way such crystals rotate during deformation. Finally the present use of quantitative pole figure methods* represents an advance over the X-ray photographic method employed by Barrett and Levenson in their work on end orientations. The present investigation provides information on the cold-rolling behavior of two groups of Si-Fe crystals: 1-—crystals initially oriented in recognized end orientations for iron crystals with a [I101 direction parallel with the rolling direction, and 2— crystals initially oriented with a [I101 direction 90" to the rolling direction and in the rolling plane. For the second group, there is a 90" range between the (001) [110] orientation and the (110) [001] orientation. Since the 35" portion of this range from (110) [OOl] to (111) Di2] was included in a previous investigation," only the remaining 55" portion from (111) fii2] to (001) [I101 needs further consideration. Also, since both (111) [xi21 and (001) [I101 are end orientations for iron crystals,' there might be a critical orientation* or orientation range be- • W. W. Martin and C. G. Dunno noted that (112) [Till was such a critical orientation. tween them such that early in the deformation an orientation within this critical range splits into two orientations. Upon further deformation, these two orientations rotate to produce a final texture consisting of (001) [1101 and (111) [?i2] components. The end orientations obtained are discussed in connection with the work of Barrett and Levenson, while the observed tendency for lateral flow of crystals in these orientations is treated in terms of the theory of Hibbard and Yen.' Lateral flow according to the theory increases with deviation of the plane containing the rolling direction and the slip direction from a position perpendicular to the plane of rolling. Experimental Procedure Single crystals in sheet form with preselected orientations were prepared by methods that have been described elsewhere." Three lots designated A, B,

Jan 1, 1956

By J. E. Ostberg, G. Phragmen, A. Hultgren, S. Wohlfahrt

Detailed study was made of a number of rimming ingots, both low and high carbon, and especially upon effects of superimposed air pressure. Requirement to suppress core bubbles is between 10 and 15 atm; at 6.5 atm freezing was in semikilled manner and at 3 atm, steel was of rising type. Probable mechanism of freezing under various conditions is discussed. AN earlier paper' reported an investigation made by a committee for studying rimming steel ingots appointed by Jernkontorets in Stockholm. The present paper is the outcome of some further work done by the same committee. Since the characteristics of ordinary rimming steel are connected closely .with the amount of gas liberated during freezing and since this amount of gas is governed by the pressure, it was considered of interest to ascertain in what manner and to what extent definite pressures applied to the top of the liquid steel in the mold would affect the solidification process and the consequent structure of a rimming steel of ordinary composition. The experiments were made at the Domnarfvets Steel Works. The steel was made according to normal practice in a 4-ton Rennerfelt electric furnace. Ferromanganese was added in the furnace; no aluminum was added, with one exception. Analyses of the four heats are given in Table I. The top-poured ingots measured about 12 in. sq x 48 in. and weighed about 1300 lb. One or two ingots of each heat were allowed to solidify under pressure, using a special device for admitting compressed air to the upper closed part of the mold, as shown in Fig. 1. A heavy plate sealed with asbestos was bolted to the top of the mold. The plate had a tapered aperture for pouring. Immediately after pouring the hole was closed by a wedged plug, and compressed air was admitted through a hole in the plug. Because of some delay in applying the plug, full pressure was not reached immediately. The pressure was adjusted to the desired value as indicated by a manometer. In order that the interior of the ingot might have the benefit of the pressure, the freezing of the top crust was delayed by a refractory lining applied to the top part of the mold, Fig. 1. Ingots were also cast from each heat without applied pressure, and with and without refractory lining at the top. Axial sections of ingots were cut either of the whole ingot or of some part of it of special interest; sections were polished and usually etched.' To facilitate description of structures the following terms may be used for different types of ingots solidified under gas evolution: 1. Box-hat or boot-leg ingot: Abundant gas evolution during casting and during rimming; no rim holes. 2. Normal rimming ingot: Lively gas evolution during rimming; usually rim holes in lowest part of

Jan 1, 1952

By Raymond A. Bradbury

The first diesel-powered Scooptram has now been in service for 21/2 yr at the I-C mine of Martin County Coal Corp. It has become the workhorse of the operation, being used around the clock many days. The fleet of nine 20-ton capacity Teletrams used behind three Jeffrey Heliminers now have more than 1 1/2-yr experience in the Coalburg mine. They have been exposed to some difficult conditions which, include steep grades, water, mud, and rutted roadways. These units have proven to he both rugged and powerful. The safety components and shutdown systems make these haulage units very safe for underground coal mines. A clean-burning engine, a satisfactory exhaust conditioning system, and good ventilation are the keys to maintaining a safe and healthful atmosphere for the underground operators and other employees.

Jan 1, 1976

By Robert F. Winkle

A detailed breakdown of mining costs, available to management on monthly and year-to-date bases, is mandatory for a controlled and efficient mining operation. A simple lump sum reporting of costs may indicate a profit or loss differential, but it does not allow an effective search for areas of possible cost reduction. Moreover, functional reporting is necessary on a timely basis so as to note trends of increasing costs In specific areas, which in turn allow possible preventive action by management. Definitive cost information helps to eliminate the tendency to overlook areas where cost Improvements can be made. A good cost control system points out salient operational weaknesses by: ( 1 ) allowing comparison of functional costs with similar costs of other mines and (2) pinpointing sudden increases over unit empirical costs within the organization. In general, the cost accounting structure is relatively uniform within large open pit mines, but surprisingly some systems will overlook the need for detailed breakout in comparatively high cost areas. In some other systems, unrelated costs will be lumped together, preventing careful analysis of cost accrual.

Jan 1, 1979

By C. A. O’Malley, F. W. Kinsey

This paper deals with an experimental study in the use of a preagglomerated burden as a means of increasing the production of sinter. The effect of a wide range of sinter burden was studied, including concentrates produced by a flotation process. Some of the important characteristics of a sinter bed are discussed along with the strength and reducibility of the sintered product. In recent years the use of sinter in blast furnaces has become increasingly important across the country—largely because of the demand for more hot iron from existing plant capacity and the increasing amount of fines in the burden materials available to the blast-furnace operator. In many instances, unfortunately, the demand for sinter has been so great that little time has been available to give the proper

Jan 1, 1960

By L. W. Rowe, W. R. Opie

A brief history of TiCI, production and purification is given. Chlorinator feed materials for the production of TiCI4 are classified. The thermodynamics and kinetics of Ticl4 production by chlorination of TiO2 are discussed. Problems encountered in the chlorination and purification steps are outlined in detail. MOST of the current processes for the production of titanium metal require the use of TiC14 as a source of titanium values. This material can only be produced by a dry chlorination process, since it is immediately hydrolyzed in the presence of water. When pure, the tetrachloride is a colorless liquid boiling at 136°C. It fumes readily in moist air, reacting immediately with the moisture to form TiO, and HC1. History The tetrachloride was prepared as early as 1826 by DumasL who chlorinated a red hot mixture of carbon and TiO,. Since then, numerous other mixtures have been used including rutile, ilmenite, beneficiated ilmenites, titanium pigment, slags, and the various titanium metalloids such as TiN, TiCN, TiOC, and TiS2. S2Cl2, phosgene, and CC14 have been substituted for chlorine and CO has been used in place of carbon.

Jan 1, 1956

By M. M. Fine

THE problem of producing a uniform, medium-fine sand for glass-furnace feed has been of interest to the glass-container industry for many years. In the present investigation of the problem, conducted by the Bureau of Mines in cooperation with the Owens-Illinois Glass Co., Alton, Ill., a satisfactory method of producing such sand was developed. The investigation involved continuous-grinding studies of glass sand with flint and porcelain pebbles, steel balls and rods, and a simultaneous study of classification. The most satisfactory procedure consisted of grinding in a pebble or ball mill followed by a double classification: hydraulic classification to separate the oversize for return to the grinding unit and mechanical classification to remove fines and impurities from the ground sand. The proper application of this flowsheet usually yielded a graded sand containing less iron than the feed even when grinding was done in a steel-lined ball mill. The amount of sand ground into the so-called "dusting" sizes was, in all cases, less than 10 pct. Experiments were made which showed that this very fine sand could be beneficiated to a usable material. Background The advantages in utilizing a uniform, medium-fine sand as a feed for glass furnaces has motivated a considerable amount of research on the ,problem of producing such sand by glass producers and others. For the glass producer, the faster melting rate of such a graded sand offers the possibilities of reduced fuel costs and increased furnace capacity. In addition, there is the likelihood of improving the quality of the melt and thereby reducing the number of seeds (air bubbles) and stones (unrnelted grains) in the finished ware. Although the melting rate of a glass batch depends on other factors in addition to the grain size of the sand, there is experimental evidence to show that grain size influences the melting rate considerably. Potts, Brookover, and Burch' found that when the raw materials (sand, soda ash, and limestone) were always matched in- size, there was a great decrease in the melting time as the grain size of the materials was decreased. They found, too, that when the grain sizes of the soda ash and Limestone were held constant at 40 to 60 mesh, the minimum melting time occurred when 40 to 60 mesh sand was used. The increase in melting time with decrease in grain size beyond 40 to 60 mesh was due, they postulated, to accelerated demixing or separation of batch during melting as the grain size of the sand decreased in relation to the grain size of the other materials. An earlier investigatora found that the highest rate of melting and purifying ordinary glass was obtained when medium-size sand (0.385 to 0.120 mm, correspondingly roughly to 40 to 120 mesh) was used. Although batches containing smaller-size sand were found to fuse more rapidly, the time required to remove air bubbles from such melts actually increased the total duration of the process. Coarsegrained sand, it was stated, increased greatly the times of both melting and purifying. Although the laboratory data are difficult to confirm on a plant scale, observations by the Owens-Illinois Glass Co. indicate a higher furnace capacity of better-quality ware when a medium-fine sand is used in the batch. During the recent war, the glass producer was inclined to overlook a considerable variation in raw materials in the interest of higher production. For instance, table I shows the wide range in the amounts of various screen fractions in sand supplied by one producer to the Terre Haute plant of Owens-Illinois. The sand, from the northern Illinois St. Peter sandstone, represented material used by that plant over a period of a few years during the war. Since the war, the glass industry has insisted on

Jan 1, 1951

By Alton B. Cook, G. B. Spencer, F. P. Bobrowski

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By M. M. Fine

THE problem of producing a uniform, medium-fine sand for glass-furnace feed has been of interest to the glass-container industry for many years. In the present investigation of the problem, conducted by the Bureau of Mines in cooperation with the Owens-Illinois Glass Co., Alton, Ill., a satisfactory method of producing such sand was developed. The investigation involved continuous-grinding studies of glass sand with flint and porcelain pebbles, steel balls and rods, and a simultaneous study of classification. The most satisfactory procedure consisted of grinding in a pebble or ball mill followed by a double classification: hydraulic classification to separate the oversize for return to the grinding unit and mechanical classification to remove fines and impurities from the ground sand. The proper application of this flowsheet usually yielded a graded sand containing less iron than the feed even when grinding was done in a steel-lined ball mill. The amount of sand ground into the so-called "dusting" sizes was, in all cases, less than 10 pct. Experiments were made which showed that this very fine sand could be beneficiated to a usable material. Background The advantages in utilizing a uniform, medium-fine sand as a feed for glass furnaces has motivated a considerable amount of research on the ,problem of producing such sand by glass producers and others. For the glass producer, the faster melting rate of such a graded sand offers the possibilities of reduced fuel costs and increased furnace capacity. In addition, there is the likelihood of improving the quality of the melt and thereby reducing the number of seeds (air bubbles) and stones (unrnelted grains) in the finished ware. Although the melting rate of a glass batch depends on other factors in addition to the grain size of the sand, there is experimental evidence to show that grain size influences the melting rate considerably. Potts, Brookover, and Burch' found that when the raw materials (sand, soda ash, and limestone) were always matched in- size, there was a great decrease in the melting time as the grain size of the materials was decreased. They found, too, that when the grain sizes of the soda ash and Limestone were held constant at 40 to 60 mesh, the minimum melting time occurred when 40 to 60 mesh sand was used. The increase in melting time with decrease in grain size beyond 40 to 60 mesh was due, they postulated, to accelerated demixing or separation of batch during melting as the grain size of the sand decreased in relation to the grain size of the other materials. An earlier investigatora found that the highest rate of melting and purifying ordinary glass was obtained when medium-size sand (0.385 to 0.120 mm, correspondingly roughly to 40 to 120 mesh) was used. Although batches containing smaller-size sand were found to fuse more rapidly, the time required to remove air bubbles from such melts actually increased the total duration of the process. Coarsegrained sand, it was stated, increased greatly the times of both melting and purifying. Although the laboratory data are difficult to confirm on a plant scale, observations by the Owens-Illinois Glass Co. indicate a higher furnace capacity of better-quality ware when a medium-fine sand is used in the batch. During the recent war, the glass producer was inclined to overlook a considerable variation in raw materials in the interest of higher production. For instance, table I shows the wide range in the amounts of various screen fractions in sand supplied by one producer to the Terre Haute plant of Owens-Illinois. The sand, from the northern Illinois St. Peter sandstone, represented material used by that plant over a period of a few years during the war. Since the war, the glass industry has insisted on

Jan 1, 1951

By K. T. Aust

The relative interfacial energies of symmetrical tilt boundaries in silver of greater than 99.999 pct purity were measured as a function of orientation difference 0 between 9° and 36° about <001>. The results are in good agreement with the dislocation model of the grain boundary. The energy vs H curve may be represented by the Shockley and Read equation in the form Eoe (0.55—In 8). READ&apos; has indicated that an ideal experimental method of testing the predictions of the dislocation theory of the grain boundary would be to measure the interfacial energies of symmetrical tilt boundaries between face-centered-cubic grains that have a common <001> axis, as a function of orientation difference 0. The misfit H should be defined by a rotation of each grain through an angle of H/2 away from the boundary. Such boundaries might be expected, from geometrical considerations, to be made up of a series of edge dislocations, at least for small values of 0. Energy vs H relationships for tin&apos; and lead:&apos; were previously obtained for an asymmetrical tilt boundary separating two grains in which generally only one grain was rotated about a <001> specimen axis through an angle of H away from the boundary, the other grain remaining fixed. It is possible, however, that the boundary atoms in tin and lead may have attained a symmetrical position, in relation to the orientations of the grains on either side of the boundary, during equilibrium annealing. The two sets of measurements on silicon ferrite&apos; were somewhat better suited for comparison with theory, since the boundaries were symmetrical tilt boundaries in which the axis of relative rotation was <110> in the first series and <l00> in the second; but this alloy has a body-centered-cubic structure. Although the grain boundaries in silver" were symmetrically tilted, the axis of relative rotation was not a simple crystallographic direction, and it varied from boundary to boundary. Although the above measurements were in good agreement with the Shockley and Read equation,"&apos;: it appeared desirable to carry out experiments under the ideal conditions specified by Read.&apos; Consequently, the relative energies of symmetrical tilt boundaries in silver between grains that have a common <001> axis were measured. The technique of equilibrating grain boundaries in oriented tricrystals was used rather than the less satisfactory thermal groove method previously employed for silver bicrystals." Experimental Details and Observations The solidification and seeding techniques, described previouslyh for growing tricrystals of controlled orientations, were used to prepare tricrystal specimens from silver of greater than 99.999 pct purity. The silver was obtained from American Platinum Works, Newark, N. J., in the form of poly crystalline rods 10 cm long and 7 mm in diam. These rods were then cold worked by rolling or drawing them into suitably shaped blanks. Single crystal seeds and tricrystals were grown in a high purity graphite boat by means of a movable furnace with globar heating elements. The graphite boat was enclosed in a Vycor tube, which was first evacuated to about l00/u Hg and then filled with a static argon atmosphere. The maximum temperature outside the Vycor tube was 1250°C. A typical tricrystal specimen of silver is shown in Fig. 1. Grains B and C were grown from seed crystals with a <001> specimen axis or longitudinal direction parallel to the direction of growth and with another <001> direction perpendicular to the surface. Each of the two seed crystals was rotated 18" about the <001> specimen axis but in opposite directions away from the boundary. A symmetrical tilt boundary, therefore, separated grains B and C with an orientation difference 8 of 36" about <001>. Grain A in Fig. 1 was grown from the middle seed with a <110> direction parallel to the specimen axis and with a <001> direction inclined at 45&apos; to the surface of the specimen. The interfaces sepa-

Jan 1, 1957

By F. P. Bobrowski, G. B. Spencer, Alton B. Cook

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

C. G. Dunn (Generai! Electric Research Laboratory)— The author is to be commended on his attempt to calculate the residual strain energy from information on the dislocation density within the subgrains and a surface energy associated with the subgrains. However, much closer agreement between a calculated critical size of a nucleus and the observed size of grains that did not continue growing can be obtained if a reasonable correction is made in obtaining the energy of the surfaces of the subgrains. For example, since the sample is a single crystal with a cold-rolling reduction of 70 pct in thickness, one needs either an average disorientation for this or an average subgrain boundary energy rather than the 2.5 deg disorientation of a bent crystal, which was used by the author. From either the Laue photographs of the author or the pole density plot of Koh and Dunn 16 for a (113) [332] cold-rolled crystal the

Jan 1, 1961