Search Documents

By E. A. Anderson, P. W. Ramsey, E. J. Boyle

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944

By M. Cohen, R. T. Howard

The purpose of this paper is to direct attention to the lower part of the austenite transformation diagram, or TTT curves, where considerable uncertainty still exists as to the blending of the bainite and martensite reactions. The dissimilarities between these two low temperature transforrnations have been summarized recently by Troiano and Greninger.' Of particular importance to the present work is the fact that martensite formation, unlike bainite formation, is not suppressed by the fastest quenching rates attainable. However, most of the investigations in this direction have been concerned primarily with the start of the martensite transformation (Mg) during cooling, rather than with the quantitative aspects of the subsequent reaction on either further cooling or isothermal holding. Several years ago, Cohen2 suggested a form of transformation diagram which reconciled, at least schematically, the isothermal characteristics of the bainite transformation with the insuppressible nature of the martensite transformation. In essence, the diagram consisted of a family of horizontal lines (representing the progress of the austenite-martensite reaction during quenching) which were interrupted in point of time by the bainite family of C-curves extending down from higher temperatures. This picture received later support by metal-lographic3 and dilatometric4,5 studies, but the techniques employed were not sufficiently critical to substantiate some of the details. Elmendorf6 and Grange and Stewardi have shown that the Greninger-Troiano metallographic technique8 may be used not only for M, determinations, but for studying the course of further austenite decomposition. In fact, the latter investigators have observed the amount of martensite formed as a function of temperature below M, in fourteen commercial steels. In the present paper, the Greninger-Troiano technique has been combined with the lineal method of Howard and Cohen9 to provide a unique, quantitative treatment of the austenite-martensite reaction. Furthermore, isothermal transformations have been similarly measured on holding at temperatures above and below M., thus permitting a fairly detailed presentation of the lower part of the conventional austenite transformation diagram. Experimental Details Materials The steels, listed in Table I, were selected for study because they exhibit a satisfactory range of M. temperatures and have not received as much attention as the lower carbon grades. They were prepared as 30 lb induction furnace heats in the laboratories of the Vanadium-Alloys

Jan 1, 1949

By R. Floyd Farris

A method is presented for determining minimum waiting-on-cement time, which takes into account the differences that exist between types and brands of cements and such individual well conditions as depth, temperature, and pressure. The basis for the method was determined by laboratory tests. Being a laboratory development, several steps were required to prove its merit. The first step consisted of laboratory tests designed to determine the minimum cement strength required in wells. Basis was found for setting a minimum value of 8 Ib. per sq. in. tensile strength. Next, it was shown by laboratory tests that the time to 8 Ib. per sq. in. tensile strength may be expressed as a function of consistometer stirring time to loo "poises," the approximate relation being "the time to 8 Ib. per sq. in. tensile strength equals the time to I00 'poises' times three." Next, it was shown that the time of maximum temperature development in cement slurries, due to heat of hydration, is also related to consistometer stirring time to loo poises, but only by a factor of approximately two. It was shown also that the shut-in casing pressure will build up after cement is placed and register a maximum pressure at approximately the same time the slurry down the hole attains maximum temperature. From this and the relationships listed above, the general rule was established that minimum waiting-on-cement time (time to 8 Ib. per sq. in.) after casing cement jobs in any well is equal to the time when the shut-in casing pressure reaches a maximum, as measured from the initial mixing of cement, times a factor of 1.5. Cement plugs drilled in the field at the time prescribed by this formula were found to drill "firm to hard," thus confirming the laboratory tests. These tests prove that many of the present regulations for waiting on cement require a longer time than is absolutely necessary. Use of the method herein proposed offers the possibility of a saving of $1200 per well. Introduction The length of time allowed for cement to set after casing is determined either by state-wide rules, field rules, or self-imposed rules written into drilling contracts. In general, the time is dictated by experience and common practice. However, owing to differences in opinion and in experience of the various groups involved, waiting-on-cement time often varies from one area to the next. For example, an operator in an area where no rules exist may drill out of surface pipe at 24 to 36 hr., while another operator in another area may wait 48 hr. or more to comply with state or field rules, although the depth of the well, hole size, type of cement, and other data are identical. An even greater difference in practices will be found by making similar comparisons with respect to oil-string cement jobs. Differences in waiting-on-cement times of 36 to 48 hr. are common. Further complicating the picture is the rather common practice of allowing more waiting time for cement to set at the greater depths than is allowed at the shallow depths. This practice has existed for years in spite of the common knowl-edge1,2,3 that the temperature of the earth at the usual setting depths of surface

Jan 1, 1946

By J. W. Spretnak, R. Speiser

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

Jan 1, 1954

By Robert Wamsley, W. E. Jones

ONE of the earliest problems in the life of any community is the provision of an adequate supply of water sufficiently free from all types of contamination to be suitable for domestic purposes. Generally speaking, the location of most communities is determined to a great extent by the availability of an adequate supply of satisfactory water. For a mining camp, that consideration cannot be foremost. Here, the ore takes first place, and the men who mine it must do the best they can under the existing conditions. If there is no local source of water, it must be brought from some distant source or must be found by sinking shafts or drilling wells. Fortunate indeed is the mining company that discovers a commercially valuable ore deposit beside a never failing creek full of pure water, with sufficient water rights available, because the acquisition of water in any other manner nearly always involves not only a considerable period of time but the expenditure of considerable money. The experience of Climax Molybdenum Co. demonstrates the measures that sometimes are necessary in order to provide a suitable supply of water. The Climax mine and mill are on the Continental Divide, about 13 miles northeast of Leadville. The elevation of the domestic part of the camp varies from a minimum of 11,320 ft. to a maximum of approximately 11,550 ft. above sea level, and, as is common at such altitudes, the near-by streams that might be suitable for a water supply are small and intermittent, usually flowing only during the summer months. The only streams of any size in the immediate vicinity of Climax are the Ten Mile and Arkansas Rivers. The headwaters of Ten Mile River are on the Company's property, and its water has been used for the domestic supply. The headwaters of the Arkansas River are about 2 miles distant and have not been used as a source of supply by the company. During the past 11 years of the production of molybdenum at-Climax, the number of families living there has increased from about 45 to 283, and the population has increased from about 200 to 1200 persons. Consequently, the capacity of the water-treatment facilities, and the amount of water available, had to be increased to meet the requirements of the camp. As early as 1932 it was recognized that the water in Ten Mile River would not continue to be adequate for domestic purposes and after considerable discussion it was decided to drive a drift through the major fault in an effort to find additional water. This drift was completed in 1935 and tapped sufficient water to make the supply adequate. This water was treated in a tank underground, where lime was added, and was then piped into the domestic supply lines. At about the time this line was completed, the presence of fluorine in harmful concentrations was discovered in the water. This problem was submitted to the International Filter Co. and in November 1937 a plant of its design was put in operation for treating the water to remove the fluorine. This plant proved entirely successful,

Jan 1, 1945

By A. A. Bauer, F. A. Rough, G. H. Beatty

AS a result of recent studies, the constitution of the zirconium-uranium system has been fairly well defined. A diagram for the system is shown in Fig. 1. However, both oxygen and nitrogen are known1-3 to have a pronounced effect on the limits of both ß- and e -phase regions. It has been shown that small amounts of oxygen severely constrict the compositional limits of these phase regions in the ternary zirconium-uranium-oxygen system. A previously published tentative diagram shown in Fig. 2 illustrates the ß-phase constriction resulting from oxygen additions. Generally, iodide zirconium has been used in constitutional studies of zirconium-uranium alloys. While this is the highest purity material available, cast iodide zirconium-uranium alloys will generally average from 200 to 300 ppm 0 and from 50 to 60 ppm N. Thus, while the constitution of the zirconium-uranium system is fairly well defined, it must be realized that this definition applies to alloys containing in the vicinity of 250 ppm 0 and 50 ppm N. The present investigation was undertaken to accurately determine the boundary between the ß-plus-P and ß phases at a single temperature in the binary zirconium-uranium system by quantitatively

Jan 1, 1959

By Charles H. Breerwood, Benjamin L. Miller

From earliest recorded times, limestone has been employed in the industrial life of peoples of all sections of the world where it exists. It is widely distributed and therefore has been available in almost every country and has been employed for a variety of purposes. Its earliest use was for buildings, since it is more easily quarried and dressed than most other kinds of rocks and so could be utilized by early inhabitants, poorly equipped with tools. The next use was in the manufacture of lime, which was employed by the ancients in mortar. These two uses of limestone are still all important, but they have been overshadowed in scores of regions by literally hundreds of new applications for raw limestone or products made from it. Anyone familiar with modern manufacturing processes can quickly call to mind many industries in which limestones are essential, and new uses are continually coming to notice. Any enumeration would probably be incomplete and soon out of date. Origin of Limestone Disregarding details and unusual types concerning which often there is insufficient evidence and considerable difference of opinion, limestones have been formed by the precipitation of calcium carbonate from solution through the action of organisms, both plants and animals, or in a limited number of instances by chemical reactions without the intervention of living forms. Some of the organisms extracted the calcareous material in order to build up hard structures, either as bony skeletons or as coverings (clams, snails, etc.), whereas others in their life functions emitted substances that resulted in the precipitation of the soluble constituents outside the organisms themselves. In some instances the organisms utilized only calcium carbonate but in some cases other compounds as well were precipitated. Various materials have been found in the hard parts of animals, and for that reason it is almost impossible to find a pure natural limestone; that is, one composed entirely of CaCO3.

Jan 1, 1938

By F. M. Lewis, J. F. Myers

The selection of the proper type of flotation machine involves the consideration of a wide variety of factors. Under any condition, all types of machines will promote some kind of separation. Obviously, the correct way of deciding which type of machine is best suited for a particular problem would be to set up all types of machines and test them out in a competitive manner, but the vast number of small concentrating plants are unable to make such complete and exhaustive tests. The experience of the authors of this paper indicates that if all the factors involved in any particular problem can be determined, and if all the flotation-machine characteristics are understood, some basis for selection could be arrived at other than actual comparison. This paper is presented to show how the process factors and machine characteristics have been combined at the mills of the Tennessee Copper Co. from studies of several types of flotation machines. At the two mills of the Tennessee Copper Co. in the Ducktown Basin of Tennessee, four distinct flotation separations are made on the complex sulphide ore. Three different concentrates are produced from the ore—in the order of their importance: iron concentrate, copper concentrate, and zinc concentrate. Four different types of flotation machines are used. The selection of these four machines, for the plant operation, was based upon the study and operating experience of the machine units shown in the following list: Fagergren machine; square cell, size 56 inches Fagergren machine; level type, size 56 inches Denver machine; conical disk impeller, size 24 inches Denver machine; receded disk impeller, size 24 inches Minerals Separation Sub-A, size 24 inches Munro-Pearse deep cell, pneumatic Southwestern air machine, Hunt principle To date the study of flotation machines has been confined almost entirely to the rougher circuits. The various cleaning operations, being relatively a much simpler matter, have not been investigated so thoroughly. Table I shows a typical analysis of the two ores as well as of the mineral content.

Jan 1, 1947

By M. Cohen, R. T. Howard

It has long been realized among metallurgists that a fast, reliable method for the quantitative determination of the percentage of microconstituents in an alloy would be of great benefit in studies of equilibrium and transformation in the solid state. For example, Polushkinl has shown that the compositions of two coexisting phases in a binary system at a given temperature may be calculated very simply with the aid of two alloys lying in the two-phase field if the relative amounts of the two phases in each alloy can be determined. Recently, Grange and Stewart2 have traced the course of the austenite-martensite reaction in a series of commercial steels by making visual estimates of the percentage of martensite formed as a function of cooling temperature. The correlation of mechanical properties with structure, a subject of wide-spread current interest, is likewise dependent upon quantitative microanaly-sis. Yet, there are very few investigations described in the metallurgical literature, wherein methods of quantitative microscopy are employed. Usually, the relative amounts of the microconstituents are estimated in a qualitative or semiquantita-tive way. The authors were faced with this problem some time ago in studying the kinetics of austenite decomposition. Several aspects of this research could not be treated satisfactorily by other quantitative tools, such as specific volume,' magnetic,6 dila-tometric, electrical resistance7 or x-ray measurements.a It became necessary to find an impersonal quantitative method that could be applied to microstructures. Fortunately, it was noted that geologists and petrographers had coped with quantitative microscopy to a considerable degree in their attempts to evaluate the mineral contents of rocks. A number of excellent articles were found on this subject, and since they appear to be unknown generally to many metallurgists, the first part of the present paper is concerned with a review of the literature in some detail. With this survey as a background, the authors have adapted the so-called methods of point-counting and lineal analysis to metallography, as described in the second part of the paper. Austenite-martensite structures were selected for illustration not only because they are important in many ways, but because such fine intermixtures are notoriously difficult to estimate visually. Literature Survey Perhaps the earliest work on quantitative microscopic analysis goes back to Delesse9 (1848) who proved mathemati-

Jan 1, 1948

By P. W. Ramsey, E. J. Boyle, E. A. Anderson

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944

By M. Prats, D. G. Russell

The performance of a well in a bounded, layered reservoir with interlayer crossflow has been investigated mathematically. The system studied comprises a centrally located well in a bounded cylindrical reservoir composed of two layers of contrasting physical properties. The reservoir contains a single fluid of small and constant compressibility. In the case of a well producing at constant pressure, the production rate of the crossflow system declines exponentially after the early transient behavior dies out. For wells which produce with constant rate, the pressure-time relationship is linear following the transient. For very early production time, the production rate of the two-layer crossflow system behaves as that of the two-layer stratified system (the case in which the layers are in communication at the well only). Except for early time, in most practical cases the performance of a two-layer reservoir with cross-flow can be duplicated by that of a single-layer reservoir. The equivalent single-layer reservoir must have the same pore volume and the same drainage and wellbore radii as in the two-layer case. In addition, the equivalent reservoir must have a "kh" (permeability x thickness) product equal to the sum of the "kh" products of the respective layers in the crossflow system. If the porosity and permeability distributions are known, the production and pressure behavior of a well with and without crossflow can be predicted. From a comparison of the observed pressure or production performance of a well and the theoretical behavior, the occurrence of interlayer crossflow can be detected. INTRODUCTION When flow is possible across the bedding plane from a low-permeability layer into an adjacent layer of moderate or high permeability, the earlier depletion of the more permeable layer will cause such flow to occur. If this situation exists, the oil recovery from tight layers can be appreciable; thus, the economic ramifications of interlayer crossflow are apparent. The possible importance and extent of flow between adjacent and connected layers — whether resulting from capillary, gravitational, or viscous forces — have been the subject of considerable speculation for many years. Jacquard1 presented a rigorous analysis of the crossflow due to single-fluid expansion occurring between two adjacent and connected layers when the well produces at constant rate. His presentation was entirely mathematical, however, and no numerical results from evaluation of the mathematical solutions were presented. Our objectives in the preparation and presentation of the present paper are essentially twofold— (1) to analyze the behavior of a well which produces a single compressible fluid from a bounded, layered reservoir with interlayer crossflow, and (2) to present practical numerical results and simplified formulas to facilitate engineering analysis of reservoirs with crossflow. The constant-terminal-pressure case was analyzed rigorously, whereas the constant-terminal-rate case was treated only for semisteady-state conditions. DESCRIPTION OF THE IDEALIZED TWO-LAYER RESERVOIR The reservoir to be studied is assumed to be bounded and cylindrical in shape, with a completely penetrating well at its center. The reservoir is composed of two adjacent horizontal layers between which fluid is free to flow. Each layer is assumed to be homogeneous, isotropic and completely filled with a fluid of small and constant compressibility. The total thickness of the reservoir is small enough

ALABAMA. Anniston.-Noble, A. E., 20th St. and Wilmer Ave. Auburn.-Brown, R. L., Box 0. Belle Ellen.-Hutcheson, W. C. Bessemer.-Abbott, C. E., T. C., I. & R.R. Co Dobbs, G. G., Box 97. Ferguson, V., U. S. C. I. Pipe & Fdy. Co. Williams, E. P., Tenn. C., 1. & R. R. Co. Birmingham.-Aldrich, T. H. Aldrich, T. H., Jr., 406 Woodward Bldg. Allen, A. W., 1616 S. 14th Ave. Bowron, J., 1401 S, 20th St. Burbidge, T. A., Brown-Marx Bldg. Coxe, E. H. Tenn. C., I. & R. R. Co. Crawford, C. G., Tenn. C., I. & R. R. Co. Crockard, F. H., Brown-Marx Bldg. Ellis, E. E.,1515 Brown-Marx Bldg. Fairbairn C. T., Woodward Bldg. Fies, M. H., 2316 Highland Ave. Geismer, H. S., Keiser-Geismer Engrg. Co.

Jan 1, 1917

By W. C. Phalen

INTRODUCTION NOBODY will dispute the fact that the conservation in every legitimate manner of our valuable high-grade phosphate-rock deposits is a present-day problem of importance. The table and curve, given herewith, show. that during the past 10 years the exportation of high-grade rock has averaged very close to half the total output of the entire country. The bulk of this exportation is from Florida, for obvious reasons. It is plain that the deposits in this State, more particularly, are being wastefully depleted under a system of selecting the cream of the product for exportation to Europe, leaving the comparatively low-grade rock, running from 65 to 70 per cent., and under, in bone phosphate of lime, for our own n fertilizer manufacturers to work up when all the best rock is gone. In this paper the writer has endeavored to make a point of describing in some detail the important methods of production and conservation in Tennessee. These ought to prove of educational value to our American agriculturists and fertilizer manufacturers, and should result in a demand for the highest-grade rock, both for direct application to the soil and for use in making acid phosphate. It is certainly evident that the European

Jan 10, 1916

By A. U. Seybolt

The pressure-temperature relations required to maintain the existence of Si3N4 in silicon-iron of 0.44-11.7 pet Si have been partially explored. The critical data obtained have allowed the calculation of some thermodynamic quantities, and have shown evidence of an order-disorder two-phase field extending at 800°C from about l pet to 5.5 pet Si. THE presence of silicon nitride in electrical sheet, nominally about 3 1/4 pet silicon, balance iron, has been described by several authors'" but there has been some discrepancy among them regarding the identity of the nitride. Also, little has been reported on the quantitative thermodynamic prop- erties. In the work to be reported here, the nitride has been found to be more stable than described by Corney and Turkdogan." Several silicon nitrides have been described in the past, including SiN, Si3N4 and Si2N4 (see, for example, Abegg6 and Pascal7). However, the literature on nitrides other than Si,N, is all very old. No recent investigators using the more powerful tools available today have reported the presence of any nitride other than S3,N4. W. B. Hicke and L. R. Brantley8 in 1930 determined the dissociation pressure of Si3N4 which they made by reacting nitrogen

Jan 1, 1959

By M. Semchyshen, G. A. Timmons

The predominant orientation in both straight-rolled and cross-rolled molybdenum is the {100} [110] texture. Upon complete recrystallization, this same texture predominates, but there is less spread about the ideal orientation. A secondary orientation about the [111] direction as the axis develops in cross-rolled sheet. Compression-rolled sheet exhibits random orientation in the plane of the sheet. Some mechanical properties were measured at varying angles to the rolling direction to determine the effect of preferred orientation on anisotropy in molybdenum sheet which had been straight, cross, or compression rolled. THE development of the arc-cast process has made available large ingots of molybdenum from which it is possible to roll sheet of considerable size. It is anticipated that such sheet will be further fabricated by spinning, drawing, stamping, or forming. Anisotropy of physical properties caused by the preferred orientation developed in the sheet during rolling may be expected to affect the behavior of the metal when subjected to these fabricating operations. To produce a sheet which will be most amenable to the fabrication of a given shape by a particular operation, consideration should be given to the directions and magnitudes of plastic deformations produced in the operation. When possible, the rolling schedule should be controlled to develop a texture which favors the required deformation. The existence of preferred orientations in rolled molybdenum sheet has been reported by Jeffries,' Konobejewsky,' Fujiwara," Goss,' and Ransley and Rooksby." None of these investigators obtained sufficient X-ray data to permit the construction of pole figures; instead, they based their conclusions upon Debye-Scherrer patterns of a limited number of positions. Ransley and Rooksby devoted some attention to transcrystalline cleavage at 45" to the rolling direction, indicating that it is appreciable in polycrystalline material only when the crystals are in the ideally preferred condition, and that this condition is only approached if the metal has been rolled successively in two perpendicular directions. In a recent paper, Custers and Riemersmao introduced the first pole figures to describe the textures of straight-rolled and cross-rolled molybdenum sheet. To increase the knowledge concerning the generation and effects of preferred orientations in molybdenum sheet, an investigation was undertaken to determine the effects of variations in rolling schedule and annealing treatments on preferred orientation, and to correlate preferred orientations with some mechanical properties. The orientations of straight-rolled, cross-rolled, and compression-rolled sheet have been determined by X-ray analysis, both as-rolled and after recrystallization. Pole figures have been constructed to describe the textures produced by these various rolling procedures. Texture of Cast Molybdenum Ingots In the arc-cast process, molybdenum powder is pressed into a vertical column which is sintered to increase its strength as it proceeds downward into a water-cooled mold, where the metal is melted in an alternating-current arc established between the end of the formed powder electrode and the metal bath at the top of the growing ingot. Since the solid-liquid interface moves continuously upward in the mold, the crystal axes are not normal to the cold surface of the mold but have the curvature shown in Fig. la. X-ray analysis reveals that the cube axis is the fiber axis and that it is normal to the cold surface of the mold; that is, the [loo] direction is parallel to the longitudinal axis of the ingot. This substantiates recent work by

Jan 1, 1953

By Fred L. Morritz, Harold M. Manasevit, Richard Nolder, Arnold Miller

Experimental evidence is presented which confirnis the epitaxial relationship between the deposited silicon and the sapphire substrate. Four distinct modes of orientation relationships have been established. These have been shown to be Single-crystal gvowth retention as a function of surfaces oriented off ideal has been qualitatively indicated. Both full-circle goniometer X-ray techniques and replica electron microscopy have indicated varying amounts of microtwinning in the silicon. film, which may he caused by the mode of silicon formation. Parameters have been found where twin density is less than I pct. The early stages of' epitaxy of silicon m sapphire have been examined by electron-microscope techniques... and mechanisms have been proposed. THE first report of the deposition of single-crystal silicon on sapphire (single-crystal aluminum oxide) was made at the American Physical Society Meeting in Canada' by one of us and was subsequently published in the Journal of Applied physics.* This paper summarizes some of the work carried on in this area since that time, in addition to reviewing some of our earlier observations. The initial single-crystal deposits of silicon on sapphire reported were obtained on sapphire planes produced by cutting a sapphire rod perpendicular to its fastest growth direction, which is approximately 60 deg from the C axis. Direct correlations between the microstructure and X-ray data as to the single crystallinity as shown in Fig. 1 are evident. These deposits were identified as (111) silicon on the substrate oriented near the (1123) of sapphire. (Sapphire notations are designated according to the c over a ratio of 2.73.) It became evident that substrate quality and surface play an important part in successful epitaxy. For example, in Fig. 2 we observe an interesting

Jan 1, 1965

By C. J. Rosa, W. C. Hagel

An attempt is made to determine the diffusion coefficients of oxygen ions in hypostoichiometric zirconium oxide. A phenomenological theory is developed for three-phase, unidirectional volume diffusion of a gaseous species from a planar source. Knowledge about oxygen diffusion in a and ß zirconium and experimentally measured rates of movements of interfaces permit the evaluation of oxygen ion diffusivi-ties in ZrO2-x. The results conform to the relationship: sq cm per sec, for the temperature range of 875" to 1050° C. DIFFUSION coefficients of oxygen ions in stoichio-metric oxides have been studied by many investigators. The obtained results not only supplement the knowledge about the lattice-defect structures of oxides and conduction mechanisms but also provide information of technological importance. Rate processes such as oxide sintering, high-temperature creep deformation, and oxidation of metals and their alloys are directly dependent on diffusion phenomena. Unfortunately, diffusion coefficients obtained from studies on stoichio-metric oxides cannot be treated without restraints when applied to oxidation kinetics, if precise evaluations of oxidation rates are desired. Oxides formed on metals are usually nonstoichiometric and exhibit nonuniform distribution of either cation or anion vacancies across their thicknesses. Debuigne and Lehr1 extended Danckwerts'2 mathematical analyses and furnished a semitheoretical treatment for evaluating oxygen diffusion coefficients in zirconium oxide in terms of weight gain measurements during oxidation of zirconium in the temperature range 400° to 850°C. Their calculations are based on theoretical partitioning3 of the total amount of oxygen between a zirconium and its oxide phase. An inherent discrepancy appears to continue throughout their calculations. The amount of oxygen confined to the oxide phase should be corrected by multiplying the calculated oxide thickness by the inverse of Pilling-Bedworth ratio, if expansion of zirconium dioxide is taken into account. The purpose of the present investigation is to provide a new semitheoretical treatment for evaluating diffusion coefficients of moving species in hypostoichiometric oxide. The analyses are relevant to unidirectional volume diffusion. Although the presented method is quite general, its applicability will be discussed in terms of kinetic measurements from oxidation of zirconium at temperatures above the a/ß transition, for reasons stated in the later part of this paper. EXPERIMENTAL Pure, 99.93 wt pct, zirconium samples of approximately 2 by 1 by 0.35 cm were exposed to oxygen for various times at four temperature levels: 875°, 950°, 1000°, and 1050°C. High-purity, better than 99.9 vol pct oxygen was passed through a cold trap and columns containing anhydrous CaSO4 to remove residual water vapor. Before exposing to oxygen at a pressure of 500 Torr, specimens were subjected to wet abrasion on 200- through 600-grit Sic papers and polished with 1—p diamond dust. Prior to oxidizing, all zirconium samples were vacuum-annealed at 10-6 mm Hg for about 15 min at the test temperature. The temperature variation across the uniform heat zone was ±2°C from the preset value. Final polishing, for phase thicknesses measurements, was performed by using 8- and 1-p diamond dust and followed by vibrator polishing with 0.05-µ ? Al2O3 solution. Measurements of phase thicknesses were made by projection on a metallographic viewing screen. Conventional powder X-ray analyses for the oxide were employed. RESULTS Fig. 1 is an example of the cross section of oxidized zirconium. Designations of phases given below this figure are the same as those used in the three-phase diffusion system represented by Fig. 5 in the following section. Zirconium oxidized for longer exposure times showed two types of oxides: white oxide at the surface and an underlaying layer of gray oxide. X-ray powder patterns of these oxides at room tern-

Jan 1, 1969

By Henry P. Ehrlinger, James C. Bradbury

Tripoli is a naturally occurring, very finely divided form of silica found chiefly in some midwestern and southeastern states and used commercially as fillers and abrasives. Definitions Tripoli is a microcrystalline, finely particulate, more or less friable form of silica that appears to be the product of leaching of siliceous limestone or calcareous chert. The term was originally applied to a deposit near Seneca, MO, that resembled material of that name found near Tripoli In North Africa (Hovey, 1894). The two deposits were subsequently found to have different physical characteristics -the North African tripoli, now called tripolite, is a diatomite, composed of the siliceous skeletons of microscopic marine plants called diatoms; the Missouri tripoli contains no diatom remains. The term tripoli, however, continued to be used for the Missouri material and is now applied in a general way to most silica deposits similar to it in characteristics and geologic origin. In commercial trade tripoli is commonly understood to designate material from the Missouri-Oklahoma field; silica from southern Illinois, the other major producing area, is referred to commercially as amorphous silica. Each term, however, may be used commercially for material, regardless of place of origin, that has the characteristics or uses commonly ascribed to the material from one or the other major producing area. For example, in the commodity price listings, Engineering & Mining Journal routinely lists under Tripoli, prices "f.o.b. Elco, IL" and "f.o.b. Seneca, MO, and Rogers, AR," and under Silica, amorphous, prices "f.o.b. IL," and "f.o.b. bierks, AR." Amorphous silica, the commercial designation given to southern Illinois tripoli, is, like the term tripoli, a misnomer. Mineralogically, the southern Illinois deposits are composed of microcrystalline quartz, and no amorphous material has been detected during X-ray and scanning electron microscope investigations (Leamnson, Thomas, and Ehrlinger, 1969; Thomas et al., 1970; Keller, 1978). Soft silica is another term that has been applied to Illinois and Tennessee tripoli, presumably to distinguish it from the more compact Missouri material. It has also been used in the ceramic trade to distinguish tripoli from "hard" silica, or silica flour, produced by pulverizing silica sand (Heinz, 1937). Rottenstone, produced commercially in Pennsylvania, is similar to tripoli in that a major constituent is finely particulate silica, and its uses are much the same as those of Tripoli-as abrasives and fillers. The origin of rottenstone also is similar to that of tripoli-decomposition of a siliceous sedimentary rock. The parent rock is defined as a siliceous limestone (Gary, McAfee,, and Wolf, 1972; Thrush, 1968) or as shale. Heinz (1937) quotes a brief statement describing the Pennsylvania deposits -"a black impure shaly limestone grading into black shale"-but does not identify the source of the statement. For convenience, rottenstone is included with tripoli in the reporting of production statistics in US Bureau of Mines (USBM) Minerals Yearbooks. Other materials that have been called tripoli include siliceous deposits in San Bernardino County, California (USBM Minerals Yearbooks, 1934-1941) and in Nevada (Chandler, 1960). These, however, differ in composition and/or origin from tripoli and, therefore, should not be identified by the name tripoli.

Jan 1, 1983

GENERAL GEOLOGICAL DESCRIPTION The uranium mineral appraisal herein described was made for an ore deposit in New Mexico. The uranium mineralization occurs as roughly tabular to lens-shaped deposits of varying thickness within the sandstone of the Jackpile formation of Jurassic age. The mineralization occurs at several horizons within the Jackpile formation, but is not always confined to specific beds. It often transgresses across stratigraphic layers, as demonstrated when attempting correlation of uranium gamma anomalies between adjacent drill holes. Preferred mineral trends have been established in some parts of the deposit, but are not always predictable when attempting to extrapolate beyond the zones defined by drill hole sampling. MANAGEMENT OF DRILL HOLE SAMPLE DATA All of the drill hole sample data used in the appraisal were obtained from interpretation of gamma-ray logs. A brief description of gamma-ray log sampling is given in Chapter 2. Two preliminary steps are involved in preparing gamma-ray logs into sample data normally acceptable for computer manipulation. 1) The gamma analog trace produced by the downhole probe must be digitized, i.e., counts-per-second (CPS) are recorded for each 0.15 m (1/2-ft) interval across the gamma-ray anomaly. The work is usually done on a "digitizer" while following the analog trace with an electronic stylus on a special tablet or table. The other alternative is to do the work manually. Some of the newest downhole logging equipment produces a magnetic tape output which can be read by a computer. 2) The gamma-ray CPS values must then be converted to equivalent U308 assay values, taking into consideration all appropriate correction factors. The US Atomic Energy Commission, now part of the Department of Energy, developed the theory and algorithm for this conversion in the 1960's, and though the work can be done manually, it is best done with the GAMRED (gamma-reduction) computer program. Fig. 14-1 illustrates a typical analog trace produced by the probe instrumentation, including gamma-ray trace (left), self-potential electric log (center), and resistivity log (right). Fig. 14-2 shows a form of the computer output after the analog data has been digitized to 0.15-m (1h-ft) intervals and converted to percentage U308 values for the same hole. The U308 grade bar graph on the right permits rapid visual inspection of anomalous values by depth and elevation. The converted U308 sample data were next processed by the SURVEY program that assigned to each assay interval [0. 15-m (1h-ft)] an X Y Z coordinate, taking into account all deviations indicated from downhole survey information. The output file of the SURVEY program was listed on the line printer for examination by project geologists, and also became the main input file for the URAN/ COMP compositing program, which is designed to group individual 0.15-m (/-ft) U308 sample values into larger intervals representing discrete anomalous zones according to a series of specified parameters entered into the program by the user. Composite U308 intervals were computed by the URAN/COMP computer program, the logic of which may be briefly described as follows: Step 1 The program searches for the highest U308 value in the hole and builds a composite by adding the highest grade interval on either side so long as the added value is greater than a minimum acceptable grade, and the total composite, after addition, meets minimum GT (grade times thickness) constraints. Step 2 The program loops back to find the next highest assay value in the hole not already included into a composite, until all anomalies above minimum cutoff grade are composited. Step 3 Individual composites are combined if they are closer than a specified minimum waste thickness, and the resultant composite grade still meets GT minimums.

Jan 1, 1980

By G. W. P. Rengstorff, R. B. Fischer

A study was made of the effect of impurities on the bend ductility of cast molybdenum. High purity molybdenum was repared by re-melting under high vacuum. The ductility of "transverse-grain" specimens indicated that intergranular brittleness decreased with an increase in purity of the metal. THE production of as-cast molybdenum with high ductility at room temperature would make working of the metal easier and increase the usefulness of the as-cast metal. Furthermore, a .knowledge of the factors that influence the ductility of as-cast molybdenum might be applied to the problem of making fusion weldments having satisfactory room-temperature ductility. Individual grains of commercial as-cast molybdenum are slightly ductile at room temperature. However, the presence of carbides at the grain boundaries may cause the metal to fracture in a brittle manner. This behavior has been discussed.' The amount and distribution of the impurities in as-cast molybdenum would be expected, from previous research on the metal, to have considerable influence on its ductility. Some effects of oxygen and carbon on the mechanical behavior of the metal were discussed by Parke and Ham,2 Woodside,3 and Zappfe. Landgraf, and Worden.4 Parke and Ham2 found that, if a sufficient number of molybdenum oxide particles were present at the grain boundaries, the intergranular cohesion was reduced to the extent that arc-melted molybdenum would rupture intergranularly during hot forging. They also found that if the oxygen content was less than 0.003 pct, the cast molybdenum was hot forgeable. It is suspected, however, that forgeable molybdenum may contain a small amount of oxide that could reduce the ductility of the as-cast metal at room temperature. Also, there is the possibility of the unfavorable distribution of other impurities having a detrimental effect on the ductility of cast molybdenum. The results of a study of the influence of purity on the room-temperature ductility of cast molybdenum are presented here. Vacuum Arc-Melting to Produce High Purity Mo One way of determining the effect of impurities on the ductility of molybdenum is to prepare and test metal as free of all impurities as possible. Accordingly, the present investigation was undertaken with this in view. Arc melting in high vacuum (less than 0.1 micron of mercury) was chosen as the method for reducing the impurities below the concentrations occurring in commercial molybdenum. Commercial arc melting of molybdenum is carried out at about 50 microns pressure. During the arc melting, carbon and oxygen in the metal react to form carbon monoxide. By virtue of the vacuum process, the partial pressure of carbon monoxide is maintained at such a low value that the reaction greatly lowers oxygen and carbon contents. An excess of at least 0.03 pct C is used in commercial arc melting to insure that the oxygen content will be below 0.003 pct. The excess carbon remaining after the deoxidation step forms carbides on freezing. Some of the carbides precipitate at the grain boundaries and, as will be shown, have an unfavorable effect on the room-temperature ductility. In the present work, only the small amount of carbon (0.003 pct) contained in the commercial powder-metallurgy molybdenum used for melting stock was present. Partial removal of oxygen from the melt probably occurred as the result of the volatilization of molybdenum oxides, or by distillation of oxygen at the high melting tem-

Jan 1, 1953