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By H. C. Rogers, B. W. Roberts

Vanadium foils and wires, either cold-worked or recrystallized, show a ductile-brittle-ductile fracture sequence with temperature. At about 150°C the hydrogenated vanadium wires are found to be ductile. At room temperature the wires show brittle fracture, and at liquid nitrogen temperature the wires are again ductile, although to a lesser extent than found at 150°C. Hydrogenated cold-rolled vanadium foils have been found to fracture in unusually straight lines along the [100] texture directions. The hydrogen content required to show this [loo] texture fracture is limited to a few atomic percent in range. Hydrogen content above this range causes fracture to occur in random directions. PRELIMINARY experiments with hydrogenated vanadium foils indicated that the embrittling effect of the hydrogen on the vanadium, which was severe at room temperature, was reduced at both lower and higher temperatures. In order to investigate more quantitatively the ductility changes with temperature, vanadium wires were tested in tension at three temperatures. The reduction of area was measured and the fractures examined. Specimen Preparation—The material used was kindly supplied by A. U. Seyboltl in the form of M-in. rod. The nominal analysis was: 99.2 pct V assay, 0.2 pct C, 0.01 pct Si, 0.01 pct Fe, 0.015 pct Ca, 0.02 pct O,, 0.01 pct N2, and 0.003 pct H,. The specimens were 0.035-in. diam wires. These were prepared by cold-swaging the supplied rod to the final diameter without intermediate anneal. They were finished with long-bearing dies. The surface was then given a light polishing with 0 emery paper and degreased in trichlorethylene. An X-ray check indicated that the cold-swaged wire had a fairly strong [110] fiber texture. The wires were then recrystallized in vacuum in continuously pumped quartz tubes at two temperatures to give two different grain sizes. One group of wires was given 45 min at 800°C; another, 60 min at 1000°C. The microstructures in Fig. 1 show the wires after they have been electropolished and elec-troetched in 10 pct HCI. After the 800°C anneal, the vanadium grains had a diameter of 1 to 2p and there appeared to be a tendency to elongation in the longitudinal direction. However, the latter may be an etching effect. After the 1000°C anneal, the grains appeared to be equi-axed, but there was a very large spread in grain size, probably due to some impurity segregation in the wire, Fig. 1, right. The grain diameters varied between the limits of 1 to 150p. The small particles shown particularly clearly in Fig. 1, left, are also visible on the polished surface of all samples before etching and are undoubtedly carbides and nitrides of vanadium. An X-ray check indicated these annealed wires had a strong [110} recrystallization fiber texture. The hydrogenation was carried out in an iron retort with dry hydrogen flowing through it, the retort and contents being heated in a tube furnace with a hydrogen atmosphere. The hydrogenation temperature was approximately 500°C. The hydro-genation times chosen were approximately those which would be just enough to cause the vanadium to be brittle at room temperature and thus allow the greatest chance for ductility to occur at the other two temperatures. Part of the fine grained specimens were hydrogenated for 21/2 min at 490°C. Part of the coarse grained specimens were hydro-genated for 11/2 min at 515°C.

Jan 1, 1957

By P. Chiotti, E. R. Stevens

The electromotive force between pure magnesium and Mg-Zn alloys in a fused KC1-LiCl-MgC12 cell was measured over the temperature range 360° to 730°C and for alloy compositions of 0.052 to 0.635 atom fraction magnesium. The calculated activity coefficients of magnesium in the liquid alloys may he represented by the relation These data and the phase diagram were employed in calculating the standard free energy of formation for the compounds MgZn, MgZn2, and MgZn2, In the temperature range from 25° to 590°C the relation ZINC-rich magnesium alloys have been shown to be very effective in reducing various solute chlorides or oxides from fused salts such as KC1-LiC1 eutectic. Such reactions are of interest in the developinent of pyrometallurgical methods for reprocessing nuclear reactor fuels.' As the conceniration of the magnesium is increased beyond 5 to 10 wt pct the extent to which solutes, such as yttrium, lanthanum, cerium, and other rare earths, can be reduced or removed from the salt decreases. This effect is due to the resulting change in the activity of the solutes in the Zn-Mg alloy as well as the change in the activity of both the zinc and mag- nesium. The purpose of the present investigation was to determine the thermodynamic properties of the Zn-Mg system which, in addition to yielding information on the alloying behavior of these two elements, would permit a more quantitative understanding of the above reactions. Since this investigation was initiated several publications have appeared in the literature giving results on the thermodynamic properties for the liquid alloys of this system. 2-4 Kozuka, Moriyama, and Kushima3 measured the vapor pressure of zinc over four different alloy compositions by a carrier-gas technique. Eremenko and Tukashenko2 and Terpilowski4 measured the electromotive force between pure magnesium and various alloys in a fused salt cell. Earlier work has been summarized by Hultgren, Orr, Anderson, and Kelley.5 In the present investigation electromotive-force measurements were made on a cell of the type The temperature range covered for the lower-melting alloys was roughly 375° to 730°C. These data were employed in calculating the thermodynamic properties for the liquid alloys and in conjunction with the phase diagram,' reproduced in Fig. 1, were used in calculating the standard free energy of formation of the compounds MgZn, MgZn2, and Mg2 Zn11. The results obtained are compared with available data from the literature. MATERIALS AND EXPERIMENTAL PROCEDURES Materials employed were: Bunker Hill slab zinc, 99.99 pct pure; Ames Laboratory magnesium containing 13 ppm N, 195 ppm C, and trace amounts of calcium, copper, nickel, and silicon; reagent grade KC1, LiC1; and high-purity MgC12 obtained from Dow Chemical Co. The electrolyte consisting of KC1-LiCl eutectic (44.4 wt pct LiC1) to which was added 15 wt pct MgCl2, was dried in a quartz tube by heating to 340° C under vacuum for a period of 4 to 5 hr, and then passing HC1 through the salt as the temperature was slowly raised to above the melting point of the salt. After about 3 hr the HC1 was shut off and the system flushed with argon and then vacuum applied for 1 hr. The salt was finally siphoned through a sintered glass filter and cast into a Pyrex container which was sealed and

Jan 1, 1965

By Elliot P. Rexford

IN the early days of concrete construction, the question of quality of sand or gravel to be used as aggregate in concrete was given little or no consideration. If the construction engineer had sufficient quantity for his structure within a reasonable distance, he was contented and gave no thought to the possibility that the material might have adverse physical, chemical, or thermal properties which could cause future deterioration of his concrete and possible failure of his structure. Today a very different situation exists. With the building of larger and larger concrete structures, with a longer and longer life expectancy, the quality of the aggregate material has become of major importance. Even in small concrete structures aggregate quality cannot be passed off lightly and the quality of the aggregate must be such as to give the anticipated life without costly maintenance. The first question to arise in the selection of an aggregate is what makes a sand or gravel suitable or unsuitable for use in concrete, and how can its quality be judged. No one rock type can be depended upon to furnish sound durable material in all instances. Granitic rocks, for example, make very satisfactory aggregates in some cases, but they are among the most unsuitable of materials when they are fractured, weathered, or highly micaceous. Limestones make excellent concrete aggregates on the one hand, and on the other they may be unsound and lack durability if they contain appreciable clay, they may have a harmful chemical reaction with the cement if they contain amorphous silica, or they may have thermal characteristics which make them highly unsuitable for use in concrete. Each rock, gravel, or sand must be proved on its own merits for the particular job under consideration. The selection of suitable aggregate materials may be divided into two major phases, the geological phase which is carried on largely in the field, and the testing phase which of course is a laboratory problem; both are important. Very often the geological phase alone is sufficient for the selection of satisfactory aggregates for minor structures but for major structures both phases must be thoroughly investigated. Geological Phase In the southwest part of the country nearly every major rock type, igneous, metamorphic, and sedimentary, may be found with all imaginable intermediate phases and in all imaginable stages of alteration. Frequently very different rock types, different as to geological age, composition, and condition occur very close together. Alluvium and stream-bed sands and gravels will consist of many different rock types and even ledge rocks may vary radically as to texture and composition within the area of a quarry site. Some of the rocks make suitable aggregate materials whereas others are highly deleterious in concrete. Too often the good and the bad occur together and more than ordinary caution is required in aggregate selection. Aggregate Sources: Concrete aggregates are usually obtained from stream-bed sands and gravels or from ledge rocks. Each has certain favorable and unfavorable characteristics and it is sometimes necessary to investigate both types to determine the most suitable source for a specific structure. Stream Beds: The predominant sources of aggregate materials in southern California and Arizona are stream beds. Vast quantities of sands and gravels are brought from the mountain ranges by the rivers during times of flood but most of these streams are dry a large part of the time and hence these deposits make easily accessible sources of aggregate materials. From many standpoints stream-bed materials make very acceptable aggregates. The gravel pebbles and the sand grains are

Jan 1, 1951

By Kim C. Harden

INTRODUCTION The purpose of the following discussion is to present the state of the art of solution mining. Since the economics of a mining method ultimately determines its applicability and viability this presentation shall revolve around the costs of in- situ solution mining. First the assumed physical characteristics of the hypothetical ore body are described, followed by the appropriate operating assumptions. Then after a brief discussion on the type of surface plant to be used, the assumed project time tables and costs for Texas and Wyoming are presented. Finally, the economics of in-situ uranium leaching are analyzed through the use of discounted cash flow rate of return analysis. ORE BODY CHARACTERISTICS The assumption of the ore body characteristics is probably the most variable portion of this discussion. The characteristics that have been used are based mainly on state of the art technology, however, consideration of the most common depths of ore, ore thicknesses, and permeabilities also influenced these assumptions. In addition, it is assumed that these assumptions are equally applicable to Texas and Wyoming. The average grade of the ore is assumed to be .09% U308 with no apparent disequilibrium. The average thickness of ore is 2.29 m (7.5 ft) which results in an average grade-thickness (GT) of .675. The assumed depth to the top of the ore is 121.92 m (400 ft), the ore density is placed at 1.78 gm/cc (18 cu ft/ton), the porosity is estimated to be 28% and the permeability 1 darcy. These assumed ore body characteristics are shown in Table I. In addition, it is specified that the costs to be later discussed are based on a minimum GT cut-off of 0.15. It is more common to use GT cut-offs of 0.30 to 0.50 but GT cut-offs as low as 0.15 in conjunction with a minimum grade of 0.05% U308 have been used in the past with success and is considered state of the art. The ultimate percentage of uranium recovered from the ore is left to the discretion of the reader since the costs and economics are based on pounds recovered by the surface plant. OPERATING AS.SUMPTIONS An annual production rate of 200,000 lbs U308!yr was chosen for this example. In order to maintain this production rate, based on the ore body characterized above, a flow of 4731 liter/min (1250 GPM) with a recovery solution grade averaging .039 gm U308/liter is assumed. A regular 5 spot well field pattern is used with a well spacing of 21.5 m (70.7 ft) between like wells and 15.24 m (50 ft) between unlike wells. This well spacing gives each well an area of influence equal to 232.25 sq m (2500 sq ftl. An excess wells factor of 1.17 is used to estimate additional monitor wells and well field boundary wells. Each production well is expected to yield an average flow rate of 37.85 liter/min (10 GPM). In addition it is assumed that the ore body has a good shape in that it is not tenuous and narrow but has at least an average width of 200 ft. The process chemistry required for this ore body is assumed to be based on the sodium carbonate System- Oxygen is the chosen oxidant. Sodium chloride elution followed by precipitation with hydrogen peroxide makes up the remaining portion of the process. A fluidized up-flow ion exchange system is specified. The operating assumptions are listed in Table II. Restoration of the ore body shall be assumed to be accomplished through the use of ground water flush. Other methods may be considered as having to fall within the costs estimated for a ground water flush in order to be economic. In Texas it is assumed that a high capacity disposal well (200 GPM +I is required and in Wyoming evaporation ponds covering approximately 35 acres are to be used. No specific cost has been given to restoration. Instead only the additional capital investment for restoration equipment is given. Then, one year of restoration operating expense is estimated and included as the operating expense for one year beyond the last pound of U308 produced. It is also assumed that restoration will be pursued in the mined out areas of the ore body contiguous with ongoing production.

Jan 1, 1980

By Elliot P. Rexford

IN the early days of concrete construction, the question of quality of sand or gravel to be used as aggregate in concrete was given little or no consideration. If the construction engineer had sufficient quantity for his structure within a reasonable distance, he was contented and gave no thought to the possibility that the material might have adverse physical, chemical, or thermal properties which could cause future deterioration of his concrete and possible failure of his structure. Today a very different situation exists. With the building of larger and larger concrete structures, with a longer and longer life expectancy, the quality of the aggregate material has become of major importance. Even in small concrete structures aggregate quality cannot be passed off lightly and the quality of the aggregate must be such as to give the anticipated life without costly maintenance. The first question to arise in the selection of an aggregate is what makes a sand or gravel suitable or unsuitable for use in concrete, and how can its quality be judged. No one rock type can be depended upon to furnish sound durable material in all instances. Granitic rocks, for example, make very satisfactory aggregates in some cases, but they are among the most unsuitable of materials when they are fractured, weathered, or highly micaceous. Limestones make excellent concrete aggregates on the one hand, and on the other they may be unsound and lack durability if they contain appreciable clay, they may have a harmful chemical reaction with the cement if they contain amorphous silica, or they may have thermal characteristics which make them highly unsuitable for use in concrete. Each rock, gravel, or sand must be proved on its own merits for the particular job under consideration. The selection of suitable aggregate materials may be divided into two major phases, the geological phase which is carried on largely in the field, and the testing phase which of course is a laboratory problem; both are important. Very often the geological phase alone is sufficient for the selection of satisfactory aggregates for minor structures but for major structures both phases must be thoroughly investigated. Geological Phase In the southwest part of the country nearly every major rock type, igneous, metamorphic, and sedimentary, may be found with all imaginable intermediate phases and in all imaginable stages of alteration. Frequently very different rock types, different as to geological age, composition, and condition occur very close together. Alluvium and stream-bed sands and gravels will consist of many different rock types and even ledge rocks may vary radically as to texture and composition within the area of a quarry site. Some of the rocks make suitable aggregate materials whereas others are highly deleterious in concrete. Too often the good and the bad occur together and more than ordinary caution is required in aggregate selection. Aggregate Sources: Concrete aggregates are usually obtained from stream-bed sands and gravels or from ledge rocks. Each has certain favorable and unfavorable characteristics and it is sometimes necessary to investigate both types to determine the most suitable source for a specific structure. Stream Beds: The predominant sources of aggregate materials in southern California and Arizona are stream beds. Vast quantities of sands and gravels are brought from the mountain ranges by the rivers during times of flood but most of these streams are dry a large part of the time and hence these deposits make easily accessible sources of aggregate materials. From many standpoints stream-bed materials make very acceptable aggregates. The gravel pebbles and the sand grains are

Jan 1, 1951

By A. E. Wraith, N. J. Petch, J. D. Embury, E. S. Wright

The two most important parameters controlling the fracture behavior of a solid are its intrinsic properties, e.g.,grain size, and the operative stress system. The latter may be modified in laminates by the presence of weak interfaces. This is studied in notch-impact tests on a mode1 system of mild steel laminates containing a variety of interfaces. The effect of these is evaluated in terms of the ductile/cleavage transition. Two laminate geometries are distinguished, here called "crack-arrester " and "crack-divider". In both, cleavage is inhibited. This arises because of relaxation of a state of triaxial tension. In the crack-avrester laminates, cleavage initiated at a notch is confined to the layer containing the notch. In crack-cliuider laminates, a thick specimen behaves as the Sum of a number of thinner ones. Additional benefit may derive from improved intritnsic propevties of- the lanlinate layers arising from greater deformation in their manufacture. It has long been recognized that the two most important parameters controlling the fracture behavior of solids are their intrinsic properties (e.g., grain size friction stress,3 distribution of second phase particles4) and the operative stress system under which fracture occurs. In solids that show a ductile/cleavage transition, cleavage is favored by the presence of a notch. This is because triaxial tensions, generated by the localized plastic constraint at the notch, are operative when fracture occurs.= Anything that suppresses these triaxial tensions will be unfavorable to cleavage. Such suppression may possibly occur in laminates containing weak interfaces and the purpose of the present paper is to explore this possibility. Two basic laminate geometries, here termed "crack-avrester" and "cvack-divider", are examined. They are illustrated in Fig. 1. With the crack-arrester laminates, there is the possibility that, when the fracture crack approaches the interface, this, if weak, may delaminate due to the tensile stress acting parallel to the plane of the crack.= If this happens, energy will be used in delamination, the crack will be completely blunted, and the triaxial tension associated with the crack will be relaxed. To fracture the second portion of the laminate, crack reinitiation will be necessary and, because of the relaxation of the triaxial tension, this reinitiation will occur under conditions of nearly uniaxial tension, which are unfavorable to cleavage. Thus there is the possibility of cleavage suppression in the second and subsequent subunits of a crack-arrester laminate. With the crack-divider geometry, there is again the possibility of delamination at the interfaces. This will divide the crack into a series of cracks propagating through the individual laminate subunits. If these are sufficiently thin, the triaxial tension will be relaxed towards a state of biaxial tension in each of them. Thus, with the crack-divider laminates, there is again the possibility of cleavage inhibition. In the present work, these possibilities are explored using a notched impact test on mild steel laminates bonded with soft solder, silver solder or copper. Even if delamination does not occur, it is still possible that cleavage may be inhibited in laminates. With the crack-arrester geometry, the cleavage crack in the first layer may be blunted and arrested by plastic deformation in the laminate bond, if this is ductile. Partial relaxation of the stress transmitted ahead of the crack into the second layer will then result and this will reduce the significance of this stress in the fracture of the second layer. With the crack-divider geometry, there cannot be much effect in the absence of delamination unless a large amount of energy is absorbed in rupturing the ductile material. EXPERIMENTAL DETAILS The composition of the mild steel (wt pet) was: 0.04 C, 0.29 Mn, 0.01 Si, 0.006 P, 0.008 S. "As-received" plate was annealed for 2 hr at 900°C and slowly cooled to give a grain size of 0.04 mm. The laminates were made by brazing or soldering together mild steel plates 8 by 3 in. by various thicknesses. These were obtained from the annealed plate by machining, so that the intrinsic material properties were .kept constant. Laminates containing two to six steel layers were studied using standard Charpy V-notch specimens cut from the bonded plates. Standard homogeneous specimens from the annealed plate and subsize ones from the laminate components

Jan 1, 1968

By W. F. Mullen, C. W. Stickler

WITH few exceptions, unit operations in the Pennsylvania slate industry in 1950 did not differ appreciably from production methods described by Behrel and Bowles2-4 several decades ago. Many traditionally picturesque but relatively inefficient hand operations continued to contribute to high operating costs in an industry in which the margin of profit, for various reasons, was admittedly low. As part of a general program in which the Pennsylvania State College has been assisting the slate industry to solve some of its problems, time and method studies were used in an effort to determine the bottlenecks of production flow. The results are as applicable to other stone industries as they are to slate. A study of the basic elements in the production of roofing slate, structural slate, and slate blackboards among selected slate producers revealed comparatively few refinements. Any marked difference in operating method was characterized largely by the available equipment, a noticeable difference in the working properties of the rock quarried by a particular company, and by either the habit thinking or ingenuity of the individual operators. With the hope that significant economies in manufacture might result, all the unit operations were broken down into elements for study and analysis. The greater part of the study encompassed those operations from the quarry rim to the finished product; however, to obtain a reasonable synthesis of time allotments per operation, several analyses of quarrying from the finish of the wire saw cut are included for reference. The complete study of quarrying made by Bowles several years ago resulted in the introduction of the wire saw into the operation; there appears to be a need for as fundamental a change in the processing of finished slate as the wire saw was in the quarrying process. Fig. 1 illustrates the flowsheet of quarried rock from the parent bed to the quarry rim with the basic elements which contribute to the difficulty of removing slate from the ground. In Pennsylvania roofing slate is produced by one of three procedures, many operations of which are quite similar. In the traditional or classical method the quarried rock is reduced by sculping and auxiliary manual treatment to workable size and then is split and dressed (trimmed to size) in the conventional shanty. Archaic as this method might appear, there are several elements that result in substantial savings over more mechanized operations. In a modified version of this method, the block is reduced by sawing and gouging preparatory to splitting and dressing in indoor stations. This method is particularly adaptable to rock which fractures unevenly by conventional sculping methods. In the third and more modern method, reduced block received from the block maker is diamond-sawed to length and finished on a production line. Fig. 2 illustrates the flow pattern in each case. In the modified and more modern plans, dressing is done on mechanically-operated trimming machines, which appreciably reduce the fatigue factor of the operator. However, it should be noted that it is advantageous for the operator to be able to control the speed of the knife to prevent breakage of certain classes of stock. In the classical plan the splitter and dresser normally act as blockmakers also and carry their eighter slabs (equivalent in thickness to eight shingles) into the shanties themselves, all of which adds to fatigue and reduced efficiency. The extremely low investment and operating expense of the classical method has undoubtedly been of paramount importance in its continuation. Production of Mill Stock The production of mill stock is accomplished by less picturesque methods than enter into the production of roofing slate but it is, in the main, relatively more efficient because of the increased use of machinery for handling and for finishing. Mill stock can be classified into two categories as far as difference in production method is concerned: structural slate and blackboards. The significant difference in operation is caused largely by the nature of the rock used for each product with the best and easiest cleaved rock being reserved for blackboards to permit the splitting of large slabs to as little as 1/2 in. in thickness. Structural stock, on the other hand, is split into panels no thinner than 11/2 in. and

Jan 1, 1952

By Joseph B. Story, John T. Clarke

A modification, of the Kelvin bridge using an inductor was used to measure the conductivities of molten sodium chloride, calcium chloride, and mixtures thereof. A capillary-type four-lead fused quartz dipping cell was constructed. The effect of a small amount of potassium chloride on the conductivity of the melt was determined. IN the electrowinning of sodium and chlorine from sodium chloride in Downs cells, calcium chloride is added to the sodium chloride in an approximately equimolar amount to permit cell operation at a lower temperature. This lower temperature improves current efficiency and ease of operation, but decreases voltage efficiency by decreasing the electrical conductivity of the melt. A knowledge of the electrical conductivity of the Downs cell melt is necessary to the understanding of Downs cell operation, for the IR voltage drop across the melt is responsible for a significant part of the electrical power consumed by the cell. The work of previous investigators on fused sodium chloride-calcium chloride mixtures was reviewed from the standpoint of consistency with the results of others on the conductivities of the pure constituents. The electrical conductivity of pure fused sodium chloride has been established with accuracy by Van Artsdalen and Yaffe,1 by Edwards, Taylor, Russell, and Maranville,2 and by Lee and Pearson.3 It has also been studied by a number of other investigators.4-13 The best values for calcium chloride are believed to be those of Lee and Pearson,3 since the sodium chloride and potassium chloride conductivity values given by them check the best literature values. A number of other investigators have also reported values for calcium chloride.'-"."' Electrical conductivity data for fused sodium chloride-calcium chloride mixtures have been reported by Sandonnini,12 Vereshchetina and Luz-hnaya,18 Ryschkewitsch,11 Barzakovskii,5 and Alaby-shev and Kulakovskaya.15 Sandonnini reports no data at temperatures lower than 850°C. The conductivity values reported by Vereshchetina and Luz-hnaya, by Ryschkewitsch, and by Barzakovskii for pure sodium chloride and for pure calcium chlor- ide vary somewhat from the literature values believed to be best and the sodium chloride-calcium mixture data of these authors and of Alabyshev and Kulakovskaya (who give no data for the pure compounds) show significant variations. In view of these facts, it seemed that an investigation of the electrical conductivities of fused sodium chloride-calcium mixtures would be worthwhile. Apparatus Bridge System—The bridge used,in this investigation is diagrammed in Fig. 1. In general, the elaborations of this bridge over the simple Wheatstone bridge were for the purposes of a) eliminating lead resistances or making them accurately measurable, and b) eliminating major capacitative and inductive effects or balancing them against each other. Lead resistances in the lower arms of the bridge were kept as low as possible by making the leads short and of low resistance wire. This could not be done in the cell arm of the bridge because of the remoteness of the cell from the other bridge components and because of the high-resistance nickel or chrome1 wires used in the cell. Since maximum sensitivity is attained when the resistances of the four arms of the bridge are equal, 50-O resistors were used in the lower arms of the bridge when fused salt conductivities were being measured, and 1000-O resistors were used when the cell was being calibrated with normal aqueous KCl solution. The cell resistance was of the order of 50 ohms with fused salts and of the order of 1000 ohms with normal aqueous KC1 solution. The resistors used were non-inductive and accurate to 50.05 pct (General Radio Co. Types 500-C and 500-H). The lead resistance between point A in the cell and point E at the measuring resistor was eliminated by using the kelvin bridge principle; that is, the voltape drop across the lead from point A to point E was divided between the cell arm of the bridge and the measuring arm of the bridge in proporation to the resistaxes in the lower arms of the bridge.

Jan 1, 1958

By R. J. Wasilewski

Electrical resistivity variation with temperature was measured on a series of alloys containting up to 33 at. pct of oxygen over the range 77° to1500°K. The resistivity behavior is highly anomalous and itzconsistent with simple metallic conduction. Both composition and temperature-depended resistivity singularities were observed. A few experiments carried out on Ti-N and Zr-O alloys indicate the presence of similar anomalies. These observations, together with the published data on effects of substi-tutional alloying on the resistiuity of titanium, suggest that the anomalies are inhevent in the electron structure of this group oj metals. The existence of two-band conduction, and a significant shift of bands relative to each other with temperature and/or the electron concentration are suggested. CONSIDERABLE advances have been made in recent years in the alloy theory of simple metals. Very little, however, is known about the bonding in transition metals and their alloys.&apos; Titanium, with its relatively few electrons, may be expected to show simpler alloying behavior than the more complex transition elements. Its alloys with the interstitial elements appear particularly attractive in an investigation of bonding characteristics because of a) the simple nature of the solute elements, b) the remarkable similarity between the equiatomic structures Tic, TiN, and TiO, and c) the extensive solid solubility ranges of oxygen and nitrogen in a titanium reported.2,3 The Ti-O system was chosen for the most extensive investigation because of the relative ease of preparation of suitable specimens. Since the main object of the work was to obtain data on the bonding and its changes on alloying, electron-sensitive properties were primarily investigated. The present work describes the investigation on the electrical resistivity-temperature-oxygen content relationships. A few experiments were also carried out at selected compositions in the Ti-N and Zr-O systems. EXPERIMENTAL Materials and Method. Polycrystalline specimens were prepared in the form of hairpin strips some 50 by 5 by 0.15 to 0.50 mm by direct metal-gas reaction. This was carried out by controlled oxidation followed by a homogenizing anneal at a higher temperature. All the test specimens were fully homogenized as judged from the uniform microstructure and microhardness. To avoid preferred orientation, each strip specimen was annealed in the ß range prior to the oxidation, this procedure assuring random orientation in the strip;4 hence any texture resulting from the oxidation reaction itself affected all the specimens to a similar extent. Titanium used was of high purity (66 DPN, 10 Kg load; major impurities 0,-43G ppm, N,-70 ppm, C-25 ppm, Fe-14G ppm). The solute content of the alloys was determined by weighing, after the reaction with a known amount of oxygen. The specimens in which the discrepancy between the volumetric and gravimetric measurements exceeded 2 pct (or 0.2 mg for the low oxygen alloys) were rejected. The mean between the two measurements was then taken as the oxygen content of the alloy. Check analyses showed no measurable nitrogen contamination. All oxygen contents are given in atomic percent. Zr-O alloys were prepared in identical manner from hafnium-free crystal bar metal, cold-rolled to strip 0.25 mm thick. Ti-N alloys required very long reaction times at the maximum temperature available (1250°C). In order, therefore, to detect possible oxygen contamination, duplicate specimens were reacted in every experimental run, and one of these was analyzed both for oxygen (vacuum fusion) and for nitrogen (Kjeldahl). Only the specimens in which the check analysis showed < 1000 ppm O were then used for resistivity investigation. Since only relatively high nitrogen alloys (7.1 at. pct; i.e., 2 wt pct N,) were investigated, this oxygen contamination was considered permissible. Dc resistance was measured by the four-probe method as previously described.= The temperature was determined with a calibrated thermocouple placed in the center of the specimen hairpin. The errors in the specimen resistance values thus obtained were estimated at 1 pct due almost exclusively to the finite thickness of the potential wires and the consequent uncertainty as regards the true resistance length of the specimen. For the calculation of the specific resistance, however, no dimensional measurements could be carried out on most of the

Jan 1, 1962

By AIME AIME

ALFRED WILLIAM GAUGER ??Al" or &apos;?Doc" to his many friends in the coal and chemical industries- is known for his research talents and organizing ability. Appropriately the first public recognition of his technical ability was by the A.I.M.E. in the publishing of a paper by George A. Burrell and Alfred W. Gauger in the "Transactions" for the year 1916. "Al" Gauger was born at St. Paul, July 31, 1892. He graduated in chemistry at the University of Minnesota in 1914. A year later he began his initiation into the mysteries of coal mining when he joined the safety division of the U. S. Bureau of Mines at Pitts- burgh, serving from 1915 to 1917.

Jan 1, 1944

By A. E. Bibb, J. R. Fascia

Single-crystal wafers of zirconium have been exposed to 680°F neutral water. The single crystals were of known orientation and weight-gain data as a function of crystal orientation were obtained. These data show that all the crystal faces studied obeyed a cubic rate law out to the time of transition whereupon the crystals corroded at an approximately linear rate. The time to transition varied from 114 days for (1074) crystals to about 325 days for the (2130) faces. The epitaxial relationship be-tween metal and monoclinic oxide was found to be (0001) H (111) and [1120] 11 [101]. A black tight adherent oxide layer was formed on the crystals in the pretransition range. This black oxide was found to be monocrystalline. The white corrosion product produced after transition was found to be polycrys-talline but highly oriented. X-ray line-broadening studies found that the black oxide was a highly strained structure whereas the white oxide was relatively strain-free. These results indicate a strain-induced re crystallization or fragmentation accompanies the change from protective black oxide to nonprotective white oxide. ZIRCONIUM alloys have been used quite extensively in high-temperature aqueous environments. Alloy additions can be made to commercial sponge zirconium which enhance the corrosion resistance of the zirconium in both water and steam media, which raise the tolerance limit for certain impurities detrimental to corrosion resistance, and which reduce the amount of free hydrogen pickup during corrosion. The development of the corrosion-resistant zirconium alloys has been a long and tedious job involving trial and error methods. This technique has been necessary because of a lack of fundamental data and hence understanding of the corrosion mechanisms. The objective of the work described herein was to provide some fundamental data with respect to the aqueous corrosion of zirconium crystals as a function of the orientation of the exposed surfaces. Hg. The zirconium chunk was then cooled to below the transformation temperature (862°C) and reheated to 1200°C for 8 hr. The ultimate size of the zirconium grains increased with the number of cycles. Rapid or even furnace cooling through the transformation temperature produces a considerable amount of substructure which was intolerable in corrosion experiments as it would be in the study of any crystallographically dependent property. It was found that a high-temperature a-phase anneal for approximately 4 days reduced the substructure below the limits detectable by visual or X-ray means. Crystals so produced were carefully cut from the massive zirconium chunk and oriented by standard back-reflection Laue techniques. The crystals were then mounted in a goniometer head and, by using the three degrees of freedom available, slices on the order of 0.015 to 0.020 in. were cut parallel to any desired crystal plane. These slices were then carefully polished on both sides to produce smooth flat faces, pickled to remove about 0.002 in. per face, annealed for 1/2 hr at &apos;750°C in a vacuum of approximately 10"5 mm Hg, flash pickled, and checked for orientation. The pickling solution was 45-45-10 vol pct HN0,-H20-HF and continuous agitation was provided to eliminate pitting of the slices. Any slice that was not within 2 deg of the desired orientation was discarded, and any evidence of substructure as indicated by the Laue spots was also grounds for discarding the sample. Thin slices were used for the corrosion tests because weight gain per area data could be obtained with only a minimum area exposed to the corrosive media that was not of the desired orientation. The thin single-crystal slices were of irregular shape and as a result the areas were determined by placing a crystal inside an inscribed square of known area, enlarging a picture of this assembly about X5, and tracing both the enlarged square and crystal with a planimeter. The zirconium used to produce these single crystals was crystal-bar grade, a typical analysis of which is given in Table I. An oxygen analysis on prepared crystals gave a concentration of 205 ppm. The hydrogen concentrations are believed to be less than 15 ppm due to the dynamic vacuum anneal given each crystal. Typical nitrogen values for zirconium treated in this manner are about 10 to 20 ppm. RESULTS AND DISCUSSION Single-crystal wafers have been exposed to de-oxygenated, deionized water in static autoclaves.

Jan 1, 1964

By Marshall Pease, R. J. Brandon

A UTILITY that has a large consumption of coal must insure an adequate and sound supply of fuel. The Detroit Edison Co., which has an annual coal consumption of about four million tons and spends approximately $32 million a year for coal, including freight charges, has developed a program for fuel procurement and for evaluation and selection of fuel for reliable and efficient plant operation. Fuel Procurement Coal Purchasing Division: The Fuel Supply Div. of the Purchasing Dept. combines all of the procurement functions in one group, which must maintain adequate stocks of fuel. In addition to its usual purchasing duties, the division also governs transportation, follow-up, invoice and freight bill, in cooperation with the Accounting Dept. The Fuel Div. is comprised of the fuel agent, an assistant fuel agent, a coal buyer and five coal clerks, who follow the movement of each car, initially approve freight bills and invoices, and file claims whenever there is a shortage of one ton or more. The fuel agent reports directly to the purchasing agent of the Company, and all major programs are planned jointly with the chief purchasing officer. The apparent individuality of the fuel section is necessary because of the tremendous volume of coal cars handled each day, sometimes as many as 500, which must be handled promptly to complete the fastest possible move from the mines to the plants. Determining Annual Coal Volume: Through the combined studies of a Production Dept. Load Committee and the Controller&apos;s office, accurate predictions of coal requirements for any given year are provided the Fuel Dept. from 12 to 15 months in advance. This is divided into the requirements of all individual power plants and central heating plants. This in turn determines the quantity and quality for plants whose specific fuels vary with the type of equipment installed. In the Detroit area, which has a high industrial load, early estimates of annual coal consumption usually are resolved at the end of the year within 4 or 5 pct of the original plan. Operating in a highly developed industrial area eases the task of estimating primary output; and, with the residential demands increasing in a steady and fairly well-defined pattern, the overall coal schedules are not subject to radical changes during any given year. Selecting Suppliers: At any time, but especially during or before an emergency, the coal supply factor must be made secure. This is particularly true in the procurement of utility fuel. There are always extreme quantities of so-called "bargain" coal available during the buyers&apos; markets, such as recently prevailed. These opportunistic offerings may be considered a means of averaging down overall price, rather than as a steady and dependable supply source. Coal is purchased on contract from mine operators and sales agents who have proved reliable. They are not opportunists who desert for higher dollars in times of duress; they do not fail to fulfill contracts when markets rise or overship when markets dip. The progressive operator today who is willing to expend capital to improve quality and service deserves much more consideration than a matching of short-term pennies. When a company has a high volume of annual needs, all phases of the mine supply must be considered. The mine must be able to produce the quality required at a fair price and be able to sell oversizes of coal in enough volume to screen sufficient nut and slack. It must crush coal and sell mine run at prices in line with competitive nut and slack and be willing to do so when there is no demand for prepared sizes. Determining Price: The public utility is in direct competition with any of its customers who can, if savings are guaranteed, generate their own power. Today, to a greater extent than ever before, private industry must do a better overall job than Government-controlled operations. The price of coal must be realistically balanced with the price paid by almost all industries and the railroads as well. The supply-demand ratio in coal is not difficult to discern. There is access at all times to Govern-

Jan 1, 1952

By Irving B. Cadoff, Alvin A. Machonis

The resistivity, Hall coefficient, Seebeck coefficient, and thermal conductivity were measured as a function of temperature for cation-rich alloy single crystals covering the composition range across the PbTe-SnTe system. Alloying of PbTe with up to 20 pct SnTe was found to have little effect on the energy gap. Above 20 pct SnTe the alloys were "p" type but below this range the sign could be varied by heat treatment. The lattice thermal resistivity of the compounds SnTe and PbTe is raised by alloying one with the other. Z values in the order the interesting values obtained. THE PbTe-SnTe system has several interesting features. For one, PbTe is a useful thermoelectric material and the possibility of improving its figure of merit by alloying with SnTe, an isomorphous compound, has been suggested since these pseudo-binary solid solutions generally have a more favorable ratio of electrical conductivity to thermal conductivity than either of the components.&apos; Other interesting features relate to the conductivity mechanism, band structure, and stoichiometry of the compounds and their alloys. PbTe is a semiconductor with an energy gap of about 0.29 ev2 at room temperature whose conductivity sign and magnitude can be varied from "n" to "p" by controlling the proportion of lead and tellurium with respect to the stoichiometric ratio.3 Excess lead results in "n"-type conduction. SnTe is found to exist only as a "p"-type material of relatively high conductivity. This behavior is attributed to stoichiometric deviation by Brebrick4 but Sagar and Miller proposed that the behavior of SnTe must be due in part to the presence of an overlapped band. An investigation of alloys of this system, therefore, might give additional information which would permit one to evaluate which of the two proposals is the more appropriate one. Abrikosov et al.&apos; studied the room-temperature electrical properties of these alloys and reported data for Seebeck coefficient and resistivity on poly-crystalline alloys. The present work is a more exhaustive survey of the PbTe-SnTe system. Re- sistivity, Hall coefficient, Seebeck coefficient, and thermal conductivity were measured over a wide temperature range for single crystals at 10-pct intervals of lead/tin ratio across the pseudobinary system. The relative concentration of tellurium was controlled so as to obtain metal-ion excesses in all cases. SAMPLE PREPARATION The crystals were prepared by melting elemental lead, tin, and tellurium in weighed proportions in evacuated Vycor capsules. The lead and tellurium were high-purity grades obtained from American Smelting & Refining Co. The tin was supplied by Comico. The proper calculated proportions of lead, tin, and tellurium were weighed and charged into prepared Vycor capsules prior to evacuation. The capsules were prepared from 15-mm Vycor tubing. A sharp point was worked on one end of the tube. A pyrolytic graphite coating was deposited on the Vycor walls by heating the tip to 800°C in an atmosphere of acetone-saturated argon. An additional coating of graphite was deposited on the pyrolytic coating from an Aquadag suspension. Above the coated tip the tube was reduced in diameter to form a constrictive neck. To avoid scratching the graphite coatings the charge was placed in the tube above the constriction. After a low-temperature bake, the evacuated capsule was sealed. On subsequent heating the charge melted down into the lower portion of the capsule. The crystals were grown by lowering the capsule through a Bridgman-Stockbarger furnace. The lowering rate was 1 in. per 8 hr. The upper portion of the furnace was set for 950°C and the lower portion for 800°C. In general the yield of single crystals was about 25 pct. The mixed compositions were, as expected, the most difficult to grow. The finished crystals were sectioned into 5/8-in. slices. The tip, end, and middle slices from each crystal were analyzed by X-ray fluorescence to determine the lead-to-tin ratio. The resulting values were used to plot a composition vs distance plot for each crystal. Slices were selected from each crystal, with the aid of the composition plots, to cover the complete range of compositions at 10-pct intervals. In general, the slices selected were taken from the seed end of the crystal where the longitudinal segregation (as determined from the X-ray fluorescence analysis) was a minimum. Laue single-crystal analysis and metallographic analysis was used to verify if a slice was single or polycrystal. Any grain boundaries were clearly visible in the as-cut and polished condition. In ad-

Jan 1, 1964

By A. U. Seybolt

The solubility limit of oxygen in columbium has been determined in the range between 775&apos; and 1100°C by means of lattice parameter measurements and microscopic examination. The solubility is a function of temperature and varies, in the range given above, from 0.25 to 1.0 pct O, respectively. BECAUSE of the marked deleterious effect of oxygen upon the mechanical properties of some of the transition metals, it is desirable to know something about the solubility of oxygen in these metals. The brittleness caused by oxygen in solution is particularly marked in the case of the group VA elements, vanadium, columbium, and tantalum. The solubility of oxygen in vanadium has already been reported in an earlier paper,&apos; and Wasilewski2 has given a value (0.9 wt pct) for the solid solubility of oxygen in tantalum at 1050°C. Brauer3 in 1941 investigated the Cb-0 system up to Cb2O5, but made no real effort to investigate the extent of oxygen solubility in the metal. He made the observation, however, that this solubility must be less than 4.76 atom pct (0.86 wt pct) oxygen. This estimate was made from X-ray diffraction results on the alloys CbO, CbO, and CbO; all alloys consisted of the terminal (Cb) solid solution plus CbO, but the last alloy containing 4.76 atom pct 0 showed only three very weak CbO lines. It is surprising that Brauer, by examining only three alloys, arrived at an estimate of the solubility which agrees very well with the results to be reported herein. Experimental Procedure A columbium strip obtained from Fansteel Metallurgical Products was cut into strips, 0.020x1/2x2 in. Two holes, about 3/16 in. in diameter, were made near the ends of the strips in order to hold them against a flat steel block for mounting in a General Electric X-ray spectrometer for lattice parameter measurements. The same holes were used to hang the specimens inside a fused silica vacuum furnace tube which was part of a Sieverts&apos; gas absorption apparatus. The apparatus and method of adding oxygen gas has been previously described.1 According to the supplier, the columbium obtained had the analysis given in Table I. After degreasing the samples, approximately 0.001 in. was etched from each side of the samples in order to remove possible surface impurities from the last rolling operation. For this purpose the following cold acid pickle was found satisfactory: 8 parts HNO3, 2 parts H2O2 and 1 part HF. Various Cb-O compositions were obtained up to 0.75 wt pct O by the gas absorption and diffusion technique. After the sample had absorbed all the oxygen gas added at 1000°C, an additional 24 hr was allowed for homogenization. This treatment appeared to be adequate, as shown by the linearity of the lattice parameter-composition plot. More concentrated alloys were prepared by arc melting mixtures of Cb and Cb2O5 since it was very time-consuming to make Cb-0 alloys in the neighborhood of 1 pct O, or over, by the diffusion method. When the flat strip specimens were used, they were ready for the X-ray spectrometer after cooling from the Sieverts&apos; apparatus. The cooling rate obtained by merely allowing the hot fused silica furnace tube to radiate to the atmosphere (when the furnace was lowered) was sufficiently fast to keep the dissolved oxygen in solution. Arc-melted alloys were reduced to —200 mesh powder in a diamond mortar, wrapped in tantalum foil, sealed off in evacuated fused silica tubes, and then heat treated as indicated in Table 11. The fused silica tubes were quickly immersed in cold water without breaking the tubes after the heat treatments. The tantalum foil prevented reaction between the fused silica and the sample; there was no reaction between the powdered samples and the foil at 1000°C, but some trouble was experienced at 1100°C. At this temperature level a reaction between the sample and the foil was sometimes observed, which resulted in erroneous parameter values. Experimental Results Hardness Tests: Since most of the X-ray samples were in the form of flat strip, it was convenient to obtain Vickers hardness numbers as a function of oxygen content. Compared to the V-O case,&apos; oxygen hardens columbium much more slowly, presumably because of the larger octahedral volume in colum-bium (about 12.0 compared to 9.3Å3 in vanadium), hence, requiring less lattice strain for solution. The plot of VHN vs wt pct O is shown in Fig. 1.

Jan 1, 1955

By E. F. Thomas

THE late George S. Rice was active in the inves--I- tigation of bumps, particularly in the last ten years of his career as chief mining engineer of the U. S. Bureau of Mines. Since most of his investigation was carried out in Great Britain, continental Europe, and—to a lesser extent—Canada, his thinking on prevention was influenced considerably by the experience of those countries. It is not surprising, therefore, that when he was called upon a few years before his retirement to investigate bumps in the U. S. and suggest ways to prevent them, he turned to longwall mining. A longwall method had been most successful in combating the bump hazard in mining coal under deep cover, especially in Great Britain, but the prevailing method there at the time was advancing longwall mining, which he knew was uneconomical under U. S. mining conditions. For this reason he proposed a modified retreating longwall system that he believed included the best features of the advancing method. As brought out by Rice,&apos; if the cover is 2000 ft and 50 pct of the coal is extracted, the static load on the remaining pillars will be about 4000 psi, which exceeds the ultimate crushing strength in most instances. If the pillar coal is overloaded before a pillar line is established, then the abutment zone preceding a line of extraction is no place to split pillars or extract them by any method other than an open-end system. Rice therefore advocated open-end mining, preferably by longwall, but he was willing to compromise with long-face mining if the longwall method was not acceptable. Rice&apos;s system was put into operation in a mine in Harlan County, Kentucky,3 but subsequent experience has shown that it did not take into account two important factors—avoidance of pillar-line points and maintenance of adequate development in advance of the pillar-line abutment area. For ten years after Rice&apos;s retirement the USBM did little investigation and research on bumps, chiefly because so few were occurring that there was not much cause for alarm. But in 1951 there were three occurrences involving fatal injuries, and the Bureau began a statistical survey in that year. C. T. Holland, head of the department of mines at Virginia Polytechnic Institute, was retained as a consultant. The resulting study&apos; of 117 case histories brought out these important conclusions: 1) Almost invariably the bump occurred in a locality affected by the abutment zones of one or more pillar lines. 2) In most cases the locality of the bump was influenced by the abutment zones of more than one pillar line. The term pillar-line point has been used for many years in the Appalachian region for such a situation. Point is used in the geographical rather than the mathematical sense. 3) In pillar-line extraction the following practices are safest in preventing bumps: a. The mine layout should provide for pillars of uniform size and shape along the extraction line. b. The mine layout should be planned so that no development need be done in the abutment zone of a pillar line. c. The layout should permit open-end extraction of pillar lines from the next goaf, so that it will not be necessary to resort to pocket mining, splitting pillars, or any practice that will involve driving in the direction of the goaf within the abutment zone. d. Pillars should be large enough to support area without undue roof and floor convergence before establishment of a pillar line. These are, of course, generalities, and while they are useful in laying out areas where bumps can be expected, they are of limited help in many mines that were committed to a system of mining before it was realized that they were subject to bumps. Under such conditions it becomes necessary to choose between the following alternatives: 1) Abandon the territory, except for pillars that offer no extraction problems. 2) Through experience select the pillars that are most heavily loaded, and, by augering, induce bumps from a safe vantage point so that impinged loads are relieved. This method was first developed at the Gary, W. Va. mines of U. S. Steel Corp. and later adapted to mining thick coal beds at Kaiser Steel&apos;s Sunnyside mine in Utah. No scientific method is available to determine where to drill within a loaded pillar. Although this method of unloading has worked very successfully at Gary—with one exception—

Jan 1, 1959

By M. J. Marcinkowski, E. N. Hopkins

An investigation has been made of the ß(fcc) — a(hexagonal) transformation which occurs in lanthanum using both electrical resistivity and transmission electron microscopy techniques. It has been shown that the ß phase can be retained below the transformation temperature by rapid quenching but that the sample immediately begins to transform to the a phase. The transformation is observed to nucleate in the vicinity of inclusions. Based on the above observations, a detailed model of the transformation has been advanced which involves the nucleation of an extrinsic stacking fault bounded by a pair of Shockley partial dislocations in the vicinity of some heterogeneity, i.e., an inclusion. The stress field of the resultant dislocation pair acts to nucleate extrinsic faults in adjacent planes and leads quite naturally to the B-a conversion with a minimum of strain energy induced in the crystal. LANTHANUM possesses an fcc structure ß) (8) upon cooling transforms to a hexagonal modification (a) in much the same way as cobalt. The one exception, however, is that the stacking sequence of the closest packed planes in a La is ABAC ABAC, and so forth,1 whereas in cobalt it is ABAB, and so forth, i.e., hep. Mainly on the basis of transmission electron microscopy techniques, there seems to be little doubt that the 0 — a transformation in cobalt involves a dislocation mechanism2 although its exact nature still remains obscure. Although the ß - a transformation in lanthanum is somewhat more complex than that occurring in cobalt, it was thought that its very uniqueness would be helpful in understanding fcc — hexagonal transformations in general. Such a general understanding of these transformations is important since they represent what are perhaps the simplest of the martensitic class of transformations. The experimental techniques used were those of electrical resistivity and transmission electron microscopy. EXPERIMENTAL PROCEDURE The lanthanum used in this investigation was prepared by the calcium reduction of lanthanum fluoride in a tantalum crucible under an argon atmosphere as described by Spedding et al. The residual calcium was removed by vacuum remelting in a tantalum container. Portions of the metal were then analyzed by emission spectroscopy as well as vacuum fusion. The amounts of the various impurities that were found are listed in Table I. A portion of the lanthanum ingot was swaged at room temperature into 0.030-in.-diam rod for the resistivity samples while the remainder was rolled into 0.010-in.-thick sheet for the transmission electron microscopy phase of this investigation. In order to eliminate the plastic deformation induced in the samples during fabrication, they were sealed in evacuated tantalum lined quartz capsules and annealed for 1 hr at 700° C. Specimen resistances were measured using the conventional "four-wire" technique described by MacDonald, 4 employing a type K-3 Universal Potentiometer and a standard 0.001-ohm resistor, both manufactured by Leeds and Northrup Co. By taking into account all of the possible errors in the apparatus, it was felt that the absolute resistivities of the approximately 0.87-in.-long specimens measured are reliable to 3 pct. Resistances from room temperature to 700°C were measured using a vacuum furnace. In order to avoid sample contamination by the thermocouple, chromel-alumel leads were spot-welded into a tantalum shield which in turn was welded to the lanthanum specimen. Resistances below room temperature were obtained by transferring the sample to a helium gas-filled quench tube and slowly dripping liquid nitrogen into a surrounding dewar flask. A steady reduction of temperature to about —190°C was completed in about 23 hr, and the resistances were measured at various temperature intervals. As will be shown shortly, rapid quenching from above about 350°C was sufficient to suppress the B -a transformation initially but subsequent annealing at lower temperatures leads to a partial ß --a conversion. To investigate this aspect of the transformation, the samples were suspended in the hot zone of a helium-filled furnace from which they could be rapidly dropped into the quench tube mentioned previously which was now

Jan 1, 1969

By S. D. Baumer, P. M. Hulme

IN the late thirties, the National Carbide Co. cooperated with C. E. Wood, of the U. S. Bureau of Mines, in his investigation of the relative merits of various desulphurizers, including soda ash, caustic soda, and calcium carbide. Laboratory tests showed that carbide, when it could be made to react, is an excellent desulphurizing agent for molten iron. Sulphur content can be driven to lower levels and higher extractions obtained with carbide than with actionsany of the more common reagents. Wood&apos;s results1 are shown in Table I. Unfortunately, as the Handbook of Cupola Operation puts it, the chemical fact that carbide is a good desulphurizer was of only academic interest because it was found to be extremely difficult to devise a practical means to make it react with molten iron. Calcium carbide is formed in the electric furnace at 4000°F and above, and its softening point is probably at least 500 °F above the usual working temperatures encountered in iron and steel practice. Consequently, carbide does not form a true slag but floats as a dry powder on top of the metal and only a very small portion of it ever comes in actual contact with the iron. Stirring with a rabble, or pouring the metal over the carbide, increases the efficiency only slightly. Extractions of 20 to 30 pct can be obtained in this manner, but conventional soda slag treatment can do better than this and do it more cheaply. All attempts to lower the melting point of carbide in order to obtain a reactive, liquid slag have so far proved fruitless. Directly under the arc in a metallurgical electric furnace, carbide becomes highly reactive. Excellent sulphur removal can be obtained without any slag other than a thin layer of carbide." imilarly, good results are obtained by adding small amounts of carbide to the finishing slag in double-slag arc furnace practice. To react a liquid with a solid, it is axiomatic that the liquid has to wet the solid before anything can happen. If the solid is heavier than the liquid, the problem is easy, but it becomes more difficult when the solid is much lighter than the liquid, as in the case of carbide and liquid iron. Wood recognized this problem and solved it in a unique fashion. The results shown in Table I were obtained by spinning the carbide beneath the surface of the molten iron by means of a refractory centrifuge. This technique allowed each particle of the finely divided carbide to come into intimate contact with the metal and to be wetted thereby. Wood&apos;s centrifuge technique was successful in the laboratory where it achieved excellent and consistent results. Some attempts were made to expand this method to commercial practice, but serious difficulty was encountered in obtaining a refractory centrifuge head that would be economically feasible. About this time the war intervened and the project lay dormant for several years. In 1944, it was revived. It was suggested that the carbide could be blown into the metal with a carrier gas in an attempt to eliminate the necessity for the expensive and brittle centrifuge. The idea was first tried out in a fairly large ladle of iron using natural gas as the carrier. Considerable sulphur was removed, but it was quite obvious that the use of natural gas was not practical. Attempts then were made to blow carbide into molten iron using, in turn, nitrogen, argon, carbon dioxide, air, and oxygen. The latter two gases proved unsatisfactory. Calcium evidently prefers oxygen to sulphur because in the tests calcium oxide and carbon dioxide were produced, the sulphur still being untouched in the iron. Nitrogen, argon, and carbon dioxide gave much better results, although the efficiencies and extractions were erratic, and only a few isolated tests approached the results obtained by Wood. Table II shows typical results obtained with these gases. The sulphur removals were interesting, sometimes even encouraging, but it is evident that such erratic behavior could not be tolerated in commercial practice. A number of different types of equipment, such as sand blasting machines, refractory guns, and the like can used to blow the solid into the metal. All types required relatively large quantities of gas in order to maintain the flow of solid carbide through the system and into the metal. It was observed that the bubbles of gas breaking through the surface of the metal contained quantities of unreacted carbide. The liquid metal never came in contact with these particles and if it cannot wet them it cannot react with them. The initial work had shown that carbide had great possibilities as a desulphurizer. In practice

Jan 1, 1952

By D. H. Gieskieng

THE advent of curved jaw crusher wearing plates made an approach other than segmental layout analysis desirable for prediction of capacities. For some time it had been known that the drawing board capacities of crushers using these plates had to be considerably modified by complicated experience factors to achieve agreement with results. Because these apparent capacities could be readily increased severalfold by minor crushing chamber shape changes, it was necessary that the utmost precaution be taken in predicting capacities of jaw plates modified for nonchoking, special wear characteristics, or any other reason. To this end the laboratory and field tests outlined by the author in a previous paper1 were made on Blake-type jaw crushers. The results of these tests were summarized in a simple first degree equation applicable to crushers using either straight or curved jaw plates. This equation first outlines the maximum capacity potential of a given crusher, then reduces this figure in accordance with installation circumstances by means of a realization factor. It was found subsequently that this equation, with the addition of an eccentric throw factor, is applicable to standard types of single-toggle or overhead eccentric jaw crushers as far as maximum capacity potential is concerned. However, these crushers have realization factor curves somewhat different from those outlined for the Blake type. While this paper is concerned principally with standard type single-toggle crusher capacities, the evaluation of data obtained with these machines is simplified by comparative reduction to the 10 x 7 in. Blake-type equivalents upon which the summary of the preceding paper was made. Convertibility of data from one type of crusher to the other also tends towards confirmation of both. The agreement of these data is sufficient to be considered complimentary. Consequently the feed factors, f, previously reported for Blake crushers are slightly adjusted to an average with the single-toggle crusher results. Blake-type equation: C = f.d.w.y.t.n.a.r [I] Single-toggle type equation: C = f.d.w.y.t.n.a.e.r [21 where C is the capacity in short tons per hour through the crusher, f is a feed factor, dependent upon the presence of fines in the feed, and the surface character of the jaw plates used. Values of f : Smooth Plates Corrugated Plates With normal fines 0.0000414 0.0000319 Fines scalped out 0.0000368 0.0000252 Large pieces only . 0.0000312 0.0000215 d is the apparent density of the broken product in pounds per cubic foot. (If the true specific gravity of the feed is known, 40 pct voids may be assumed and d becomes 37.4 times sp gr). w is the width of crushing chamber in inches. y is the openside setting of the crusher, in inches. In the case of corrugated jaw plates it is measured from the tip of one corrugation to the bottom of the valley opposite. t is the length of jaw stroke in inches at the bottom of the crushing chamber. It is the difference between open and close-side settings. n is rpm, or crushing cycles per minute, a is the nip-angle factor. It is unity for 26" and 3 pct greater for each less nip-angle degree. A nip-angle of 20" has an a value of 1.18, and an angle of 30" has an a value of 0.88, see Fig. 1. r is the realization factor. It is unity for perfectly uniform choke feeding and usually less for actual operating conditions according to the method of feeding used and the probabilities of hang-ups involving the size of feed and crusher opening. Approximate values are given by the curves in Fig. 2. These values are further reduced by intermittent feeding, e is the throw or diameter of gyration of the single-toggle crusher eccentric in inches. As evident in Fig. 1A, variation of feed size will generally have little effect on nip-angle if both jaw plates have flat areas. Jaw plates having continuous curvature, as in Fig. 1B will have different nip-angles, depending upon the size of feed. For test work as described in this paper this effect was accounted. For general compilation of capacities for average feeds it is suggested that the nip-angle be taken at the various settings computed, at an arbitrary level, such as is indicated in Fig. 1C. Data Evaluation To bring the Blake and single-toggle type crusher capacity test results to common terms for evaluation, all data are converted to terms of 10 x 7 in. Blake-type performance at conditions of 100 lb per cu ft, 10 in. chamber width, 250 rpm, 0.65 in. stroke, 3-in. openside setting, and 18° nip-angle. (The nip-angle of the 10x7 in. Blake is 18° at 3-in. setting.) The single-toggle crusher performances are also divided by the eccentric throw to bring this effect to unity. As outlined,&apos; laboratory and field tests made on Blake-type crushers ranging from 10 x 7 in. to 60 x 48 in. were summarized along the foregoing conditions of speed, stroke, etc. This resulted in groups of data which correspond to feeds with fines, feeds

Jan 1, 1952

By C. Laird, C. E. Feltner

May different kinds of dislocation structures have been observed in strain-cycled metals and alloys. In order to understand their pattern and causes, an experimental program has been carried out to determine the influence on the dislocation structures of the three variables: 1) slip character of the material, 2) test temperature, and 3) strain amplitude. The results show that at high strain amplitudes cell structures me formed when the slip character is wavy, and that these are progressively replaced by uniform distributions of dislocations as the stacking fault energy is decreased. At lower strains, dislocation debris is formed which consists primarily of dipoles in wavy slip mode materials and multipoles in planar slip mode materials. Temperature merely acts to change the scale of the structure, smaller cells, and clumps of dislocation debris being associated with lower temperatures. It is shown that the results for many metals fit this pattern, which Parallels that occurring in unidirectional deformation. DISLOCATION structures produced by cyclic strain (fatigue) have been examined in a number of metals by transmission electron microscopy. These studies have produced a variety of interesting and often seemingly conflicting results. For example, different investigators have reported such structural features as cells.le4 bands of tangled dislocations,4&apos;5 dense patches or clusters of prismatic dislocation loops, planar arrays,4&apos;10 and various combinations or mixtures of these different structures. Most of these observations have been made on materials which were initially annealed and cyclically strained at low amplitudes resulting in long lives. Recently we have reported observations of the dislocation structures produced in copper and Cu-7.5 pct Al cycled at large amplitudes, resulting in lives of less than 104 cycles.4 These results, examined in combination with those in the literature, have suggested that a common or consistent structural pattern exists. Variations in this pattern appear to be determined chiefly by the three variables, namely, the slip character of the material,4,11 test temperature. and the strain amplitude. To verify this interpretation, we have studied [he influence of the above three variables (in different combinations) on the resultant structures in cyclically strained metals. Copper, fatigued at room temperature, was chosen as a reference state to which all other observations can be compared. The effect of slip character has been investigated by employing fcc metals of different stacking fault energy. Thus aluminum which has a more wavy slip character than copper, and Cu-2.5 pct A1 having a more planar slip char- acter, have been examined. The aluminum samples were fatigued at 210°K thus making their homologous temperature equal to that of copper at room temperature. The influence of temperature has been evaluated by examining the structures in copper at room temperature and 78°K. Finally the effect of strain amplitude was studied by looking at the structures at amplitudes giving lives ranging from 104 to 107 cycles. All of the specimens were examined at the 50 pct life level at which stage the structures have reached a stable configuration.12 I) EXPERIMENTAL PROCEDURE Strip specimens, 0.006 in. in thickness, were prepared from base elements of 99.99 pct purity or greater. Specimens were fatigued by cementing the strips to a lucite substrate which was subjected to reverse plane bending. This method of testing has been described e1sewhere.7 After fatiguing, specimens were thinned and examined in a Philips EM 200 which was equipped with a goniometer stage capable of ±30-deg tilt and 330-deg rotation of the specimen. On the basis of separate calibrations,13 allowances were made for the relative rotation and inversions between the bright-field images and the diffraction patterns. II) RESULTS AND DISCUSSION The life behavior of the materials under different test conditions is shown in Fig. 1 in the form of plots of total strain range vs cycles to failure. Comparisons of structures produced in the different materials were made at amplitudes which produced equal numbers of cycles to failure. The influence of strain amplitude on the structures produced in the reference state material (copper tested at room temperature) is shown in Fig. 2. At the 104 life level the structure produced comprises cells similar to those previously observed.3,4 They are approximately 0.5 p in diam and the cell walls are generally more regular or sharper than those produced by unidirectional deformation.14 At the 10&apos; life level the

Jan 1, 1969

By J. B. Campbell, V. V. Valleroy, B. T. Willman, L. W. Powers

A steam drive of heavy oil was field tested in a shallow, low oil-saturation formation near Deerfield, Mo. The pilot was conducted in the Warner formation, a sandstone containing an 18&apos; API oil having 1,000-cp viscosity at the 60F origind reservoir temperature. The formation war at a depth of 160 ft. Steam was injected into nine input wells arranged in an array of inverted five-spot patterns. In the completely confined center pattern, 14 temperature observation wells were installed to obtain thermal data and observe test progress. Late in the test, slugs of ammonia were injected to trace the flow paths of injected fluids. From the test area about 7,000 bbl of oil were produced. Data were obtained on areal and vertical temperature distribution, steam front advance, reservoir fluid movement and terminal saturations. This field test of a steam drive (I) demonstrated the feasibility of the method, (2) confirmed that the low residual oil saturations observed in the laboratory are obtained in the steam-swept region in the field and (3) provided recovery and conformance data for one set of field conditions. INTRODUCTION The Deerfield steam drive pilot test was conducted in a shallow sandstone containing 1,000-cp oil. The venture was undertaken cooperatively by the research and production departments of Carter Oil Co., which organizations have since been consolidated into Esso Production Research Co. and Humble Oil & Refining Co.. respectively. The production department was interested in steam injection at Deerfield because it appeared to be the most promising method of commercially producing this heavy oil deposit. The research department was interested in applying the new recovery method and in evaluating its performance in the field. At the time the test was begun, the initial oil saturation was not well known. Subsequent air coring and early pilot results confirmed that there was too little oil in place for profitable commercial exploitation by steam. Pilot termination at that time, however, would have been premature for evaluating field performance of the process, and the tert was continued to obtain additional data on steam injection as a recovery method. The test was located in Vernon County, Mo., about 10 miles north of the town of Deerfield and only a few miles from the Kansas border. The pilot site was selected as typical of the area. The location represented neither the highest nor the lowest oil saturation region in the acreage under lease in 1954. The steam drive was conducted in the Warner sandstone of Lower Pennsylvanian age. At the test site the top of the Warner occurs at about 160 ft subsurface and the formation is a fine- to medium-grained micaceous sandstone that dips gently to the northwest at the rate of 12 to 15 ft/ mile. A cross-section and permeability profile of the test location are shown in Fig. 1. At the pilot location the average total thickness of the Warner formation is about 43 ft, but the effective thickness for steam drive is 26 ft. Two distinct types of hydrocarbon saturation are apparent. The lower portion of the total sand, averaging about 17 ft thick, contains a very heavy asphaltic material that will not flow under the influence of a steam drive. This bottom interval, referred to as a dead oil residue, was not considered as part of the net sand undergoing steam exploitation. The initial formation and fluid properties of the upper 26 ft in the test area are summarized in Table 1, and variation of oil viscosity with temperature is shown in Fig. 2. Imbibition tests on preserved core samples taken at the end of the pilot test showed that the Warner sandstone was then neutral or slightly water-wet. Initially, the reservoir may have been strongly water-wet as indicated by low relative permeability to water during both water injection testing and early steam injection. PRIOR HISTORY Initial production tests of wells at the pilot site produced water with only a faint show of oil. No gas was produced except at Well 7-W in the pilot area and at another well about 1/3 mile northeast of the pilot. Prior to the start of the steam drive, a two-well water injection test and a two-well air injection test were conducted. No oil was produced by either. Water was pumped into Well I-W in the northeast corner of the pilot area with simultaneous production from Well 1 (Fig. 3). The air-injection tat was run at input Well 9-W and its offset, Well 2, in the southwest corner. Air and water injectivities were about the same when corrected for viscosity and pressure differences.