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By C. E. Richards, C. N. Reid

The influence of preferred orientation on the incidence of defbrtnation tuinning has been studied. High-purity iron with almost vandonz grain orientation was cotnpared uitll iron of the sa)ne grain size and composilion lza,ing a strong (110) fiber texture. As expected from published work on single crgslfls, /he ))lean stress for the onset of luitzning-, and the l,olu)nt. fraclion of twinned nzaterial obserlled in lension differed fron the 1-a1ue.s it2 co?nPression for tnolerial with a slrong texlure. The llinning stress of "rctndorrl " )zalerial did not 17ary with the sense of the aPPlied unin.via1 stress, but sirprisinglg the incidence of 1c)i)zning- was about three 1i))zes greater ill conzp?&apos;ession Illon in lension. These results (Ire attributed entirely to ovienbation and may be nderslood in ler?ns of the shear slresses acting on the allowed twinning syster)is. J. HE twins most commonly formed in bcc metals may be described as regions of the crystal in which a particular set of (112) planes is homogeneously sheared by 0.707 in the appropriate ( 111) direction. A similar twin-related crystal could be produced by a shear of 1.414 in the reverse (111) direction but twinning by this large displacement has never been reported. Thus, twinning is unidirectional and a shear stress which produces twinning does not do so when its sense is reversed. The sense of a shear Stress is reversed when the loading is changed from tension to compression, or vice versa. Consequently, for a given orientation of a crystal relative to a uniaxial stress, only a fraction of the twelve (112) twinning systems are geometrically capable of operating in tension, and the remaining systems may operate only in compression. Therefore, when twinning is involved, there are expected to be differences in behavior between crystals tested in uniaxial tension and those tested in compression. This has been verified experimentally by Reid et 01.&apos; and Sherwood el al.,&apos; although a critical stress criterion was not encountered. Furthermore, twinning stresses in colmbium," tungten, tantalum,&apos; irn,&apos; i-Fe,\ nd molybdenum7 single crystals have been shown to depend critically on orientation, although again twinning did not occur at a critical value of the macroscopic shear stress. However, when twinning occurs, it generally does so on the most highly stressed systems, 1--4&apos;6&apos;8&apos;9 implying that the stress level does have some relevance to twin formation. In view of the large orientation dependence of twinning in bee single crystals, it might be expected that such an effect would be present in poly crystalline material which possesses a recrystallisation texture. Indeed, riestner" showed that the twinning stress in tension is very orientation-sensitive it1 <&apos;grain-oriented, silicon-iron;" this material possessed a very strong t c m^ii a nnr x_____k . i-_ii__ ri_______j. _x r»i_._:__i preferred orientation obtained by secondary recrystallisation. Reid et a/.&apos; observed a marked difference in the tensile and compressive yield stresses of polycrys-talline columbium which was rationalised in terms of the effect of a preferred orientation on twinning. No other such illformation is known to the authors. Several investigations of twinning in polycrystalline bcc metals have been reported in which the possible existence of a preferred orientation was not even mentioned. It is the purpose of this paper to show that there is a strong effect of texture on twinning in polycrystalline iron, and to poilt out the difficulty in eliminating preferred orientation in recrystallised metals. 1. EXPERIMENTAL METHOD Material and Specimen Preparation. Low-carbon, high-purity iron was obtained from the National Physical Laboratory in the form of $-in. diam rod which had been cold-swaged from a diam of 1 in. The composition of the material is given in Table I. The as-received bar was cold-swaged directly to 0.185 in. diam from which cylindrical tensile and compression specimens were machined. Specimen geometry is illustrated in Fig. 1. The gage length was 0.30 in. long and 0.10 in. diam; it should be noted that, apart from the extra heads which are necessary for tensile loading, the geometry and dimensions of the two types of specimen are identical. The specimens were heat treated either by sequence A or B outlined in Table 11. The essential difference between these two treatments is that in one case the material was repeatedly cycled through the y- to a-phase change in order to produce grains of almost random orientation ("random" iron)

Jan 1, 1969

By Jerry R. Riding

Metallurgical process methods have seen dramatic improvement over the past fifty years. As these improvements have come about, more and more emphasis has been placed on obtaining accurate and rapid analysis of the metallurgical processes. Well-defined conventional laboratory analysis procedures which have proven to be reliable were developed early in the mineral industry&apos;s history; however, these conventional procedures, which have not changed appreciably in fifty years, have the serious drawback that they are too slow to be of appreciable value in automatic control of the processes. For example, the assay results normally become available to a mill operator from eight to twenty-four hours after a sample is taken. Since the desired mineral separation can only be made while the minerals are in the flotation circuit, conventional assay results provide information similar to postmortem reports. Consequently, using conventional procedures, the mill is operated with information from an earlier period of time, which may not reflect current conditions. In recent years there has been a steady increase in the volume of required samples. At the same time, labor, material, and overhead costs have continued to rise causing the cost per assay to reach an alarming level. This rising cost per assay, plus the increasing demand for rapid analysis necessary for control, has caused the mining and metal processing industries to look toward other techniques to solve these problems As a result, X-ray fluorescence which can provide on-stream analysis necessary for control, as well as perform numerous laboratory assays at lower cost and at a much greater speed than conventional methods, has gained wide-spread attention. In addition, multichannel X-ray fluorescent instruments are now available which have been perfected to the point where the analysis of the most important chemical constituents is available within one minute after a sample is presented to the X-ray analyzer. Because of these obvious advantages, extensive use is being made today of X-ray analysis in the mining industry to analyze slags, ores, and mineral content of rocks. The results are used to make quick decisions for both mining and beneficiation of metals. For example, X-ray systems which provide rapid on-stream analysis of the slurries at desired points Fn metallurgical processes have recently been developed. The successful application of these systems has moved the milling process a step closer to fully automatic control.

Jan 1, 1969

By Jack L. Henry

The ternary system A14C3-AIN-Al203 has been examined to determine compositions which may display desirable high-temperature refractory properties. Powder methods were employed in the synthesis of all test compositions. Forming and sintering behavior was examined and hot-pressing parameters were measured. Several properties were studied for each composition of interest in the system. The properties included hydrolysis rate in moist air, elevated temperature oxidation rate, density, softening point, tensile strength, and rupture strength. In most cases equilibrium was not achieved, and the data are representative of a nonequilibrium system. Approximately 16 separate phases have been observed in the system. Forming behavior and selected properties of five compositions of interest were compared with those of aluminum oxide and aluminum nitride. None of the compositions compared favorably. Oxidation and vaporization appear to be serious drawbacks to the use of these compositions at elevated temperatures.

Jan 1, 1969

By M. T. Hepworth, T. P. Papazoglou

Hydrogen diffusion in hcp and bcc titanium in the temperature range 610° to 900°C was measured by reacting cylindrical specimens of high-purity titanium at constant temperature with small constant pressures of hydrogen of the order of a few Torr. In the range 0 to 6.7 at. pct H in hcp titanium, the diffusion coefficient D in sq cm per sec is given by: where T is in °K and R in cal per g-atom OK. Only three measurements of diffusivity in bcc titanium were made: at 900&apos; : the diffusivity in ß titanium was found to be 1.8 x 10-4 sq crn per sec. McQUILLAN1 has studied the constitution of the Ti-H system and reported the concentration of hydrogen as a function of pressure of hydrogen and temperature. He found hydrogen absorption was reversible and rapid at temperatures above 500°C in both crystallographic modifications, the a (hcp) phase and the ß (bcc) phase, with the latter phase stabilized by hydrogen additions. Wasilewski and Kehl 2 measured the diffusivity of hydrogen in hcp and bcc Ti-H alloys. For bcc alloys, they reacted cylindrical specimens of titanium with hydrogen gas at 1 atm pressure. They measured the rate of absorption of hydrogen isothermally on specimens ranging from zero hydrogen content when above the transformation temperature to hydrogen contents sufficient to stabilize the bcc phase when below the transformation temperature. By integrating Fick&apos;s second law for a cylindrical geometry, assuming a diffusion coefficient independent of composition, they calculated diffusivities as a function of temperature. In the range 650" to 1000°C their results in bcc titanium yielded the expression: where D is in sq cm per sec, T in OK, and R the gas constant in cal per g-atom-OK. Their studies on the hcp a phase were conducted by exposing long cylindrical titanium specimens to hydrogen at a sufficiently high pressure to establish a surface layer of fl phase 80 to 120 u thick for the duration of an isothermal experiment. Concentration profiles were then determined by hydrogen analysis from chips obtained upon machining quenched specimens. The diffusivity of hydrogen was then calculated yielding the expression: The present investigation was undertaken principally to redetermine the diffusivity data on a titanium by a direct absorption from the gas phase at sufficiently low hydrogen pressures to avoid the presence of a surface bcc phase and also to check the diffusivity data at low hydrogen concentrations in the bcc stmcture. EXPERIMENTAL PROCEDURE High-purity electrolytic sponge titanium (99.9 pct) of BHN 91 was arc-melted, forged, rolled, and machined into cylinders of final hardness, upon annealing, of BHN 92. Cylindrical specimens of two sets of dimensions were used: 1.524 by 2.931 cm and 1.905 by 3.663 cm diam and length, respectively. The experimental apparatus used for annealing specimens and for admitting known amounts of hydrogen at constant pressure is shown in Fig. 1. In a typical experiment, a specimen was lightly abraded with fine-grain silicon carbide, washed with water and detergent, and then thoroughly degreased with reagent-grade tri-chlorethylene and acetone. The specimen was suspended by a Chrome1 wire in the center of a quartz furnace tube, without contact with the tube, and heated to 925°C (as measured by a thermocouple adjacent to the specimen, outside the tube) for a period of at least 4 hr under a vacuum of from 10-6 to -7 Torr as measured by an ionization gage. The furnace temperature was then adjusted to the temperature chosen for the particular diffusion study and the specimen allowed to equilibrate thermally. Hydrogen was then ad-

Jan 1, 1969

By Michel Dupuy, Daniel Calais

The study of self-diffusion of plutonium in E phase has been carried out by the welded couples method. The tracer used was puZ4O which is detected by its X-ray emission (conversion lines of uranium which are computed between 13 and 21 kev). Intensities were measured with a scintillation counter. Each layer was removed in a direction parallel to the original interface with a grinding machine and a thickness measured with a pneumatic comparator. The concentration-penetration curves obtained were corrected for the effect of heating time from room temperature to annealing temperature and for the expansion due to phase transformations of plutonium. They were analyzed by the generalized Gruzin method. Self-diffusion of plutonium in E Phase is very fast cm per sec between 500" and 620°C) and the diffusion zones are 2 to 3 mm wide for annealing times ranging from 30 min up to 10 hr. The Arrhenius law gives the temperature dependence in the form: From the point of view of self-dqfusion, PUE phase falls into the anomalous bcc metals category (Tip , Hfp, Zrp, Uy) with a low-frequency factor and an activation energy lower than those provided by standard correlations. No theory proposed hitherto to explain these anomalies (influence of dislocations, of extrinsic vacancies bonded to inlpurities, of bi-vacancies) can clearly explain the self-diffusion coeffzcients of plutonium. DIFFUSION in bcc metals is a present-day problem. A recent symposium (Gatlinburg, 1964), followed by a book,&apos; has been devoted to it. A great many experiments seem to show that diffusion in certain bcc metals obeys unexpected laws. The activation energies measured are sometimes strangely low (B hafnium, y uranium). For certain metals (0 zirconium, p titanium) the curves of log D (D = diffusion coefficient) as a function of 1/T (T = absolute temperature) are not linear. The frequency factors Do, which are of the order of 1 sq cm sec-&apos; in fcc metals, vary from 1 to 10~6 sq cm sec-&apos;. Various theories have been put forward to explain these anomalies; none is yet satisfactory. We wished to introduce a new experimental result by studying the self-diffusion in c plutonium. This allotropic phase, stable from 475°C up to the melting point (640°C), is in fact bcc. Unfortunately, nothing is known of the characteristics of the point defects in this phase, which limits the scope of the hypothesis which can be made about the mechanism(s) of self-diffusion in plutonium. 1) EXPERIMENTAL METHODS 1) Principle. We used the welded couple method. The two pellets of the couple initially have different 240 isotope contents (X emitter). After diffusion, the concentration/penetration curves are drawn up by the generalized Gruzin method. 2) Gamma Spectrography. The metal used in our study is plutonium, either low in puZ4O (isotopic content 1 pct) or high in puZ4O (8 pct). The latter also contains plutonium 241 (-1 pct) and 300 ppm of ameri-cium produced by the reaction Pu2U-AmM1 + 8-. The emission spectra of these two plutoniums placed in leak-tight vinyl bags have been studied by y spectrograph~. The detector is a thin crystal of thallium-doped sodium iodide. The activity of the plutonium rich in 240 is about twice that of the plutonium low in 240 in the energy band of 17 kev (L conversion lines of uranium); this band was used in these measurements. 3) Preparation and Examination of the Diffusion Couples. Diffusion couples were made from plutonium with a high and low PU"&apos; content. Pellets (6 6 mm. thickness 3 mm) mounted on a polishing disc with ground parallel faces were polished mechanically on both sides. In this way, pellets with two parallel faces were easily obtained. The polished pellets were joined by a 6 phase anneal (420°C, 1 hr) in a small screw press (pressure of 20 kg per sq mm cold); a centering ring enabled the two pellets to be pressed coaxially. The couples then were subjected to the diffusion treatment by annealing in the E phase in sealed silica ampules in argon at atmospheric pressure. The annealing temperatures and times are given in Table I. The couples were encased in a mild steel ring, the joint interface being thus parallel to the ground face of the ring. The diffusion couple/ring assembly underwent successive abrasions by means of a magnetic plate grinder. The thickness of the abraded layer was measured with a Solex pneumatic comparator when it was less than 0.1 mm (accuracy 0.2 p) or with a mechanical micrometer (accuracy 3 p) for passes of the order of 0.2 mm. All these operations were done in glove boxes, as plutonium is particularly toxic. After each abrasion we determined the emission spectrum of the ground face. The emissive surface is defined by means of a diaphragm 3 mm in diam. We noted more particularly the X activity in the 17-kev

Jan 1, 1969

By Grace N. Broderick

U.S. supply and demand data for coal, by States and regions, were tabulated for the years 1960 and 1965. Estimates are provided of State-by-State quantitative data for the coal industry that can be integrated into State and regional energy balances by source, form, and consumer sectors, and used for estimates of interstate and interregional energy flows. The tables give an estimated total supply of coal available for consumption, and also report the distribution of the supply among the major consuming sectors (household and, commercial, industrial, transportation, and electricity generation). To enable comparison of coal data with those for other energy forms, tonnages were converted to British thermal units (Btu). Future energy analysis studies could be facilitated by changes in the categorization of information collected on the coal industry. The data shown are based primarily on Bureau of Mines source material.

Jan 1, 1969

By Edwin B. Wilson

Over the past several years, state governments have been vigorously refurbishing old health department agencies and smoke control laws in anticipation of pending federal developments. Many states now possess a mature air pollution control administrative organization and a fairly sophisticated set of regulations on air pollution, This developing network of state control legislation and regulation is the machinery which will be called upon to implement federal standards, In order to prevent the wasted effort and resources which inevitably result from hasty action, industry should be in con- tact with local and state control agencies and be familiar with lines of communication to agency representatives. Thorough knowledge of applicable laws and regulations, both current and pending, is required. Moreover, federal law and future federal air pollution control plans, should be well known. Industrial air pollution control should be geared to a long range plan which utilizes existing technology while at the same the recognizing that today&apos;s technology will be improved upon with time, Regulation, too, can be expected to become more stringent. The implications of air pollution control in the Appalachian region of the United States will be felt most strongly by the coal industry of this area. Either directly or indirectly most regulations in these states have a significant bearing on coal mining, processing, utilization or waste disposal. The extent of coal-related activity in the Appalachian States of West Virginia, Pennsylvania, Maryland, Virginia, Kentucky, and Tennessee can be observed from the data provided in Table I. This data indicates that 86 percent of active bituminous coal mines and 69 percent of bituminous coal production were accounted for by these states. The purpose of this paper is to provide information on current and proposed legislation and regulations on air pollution in the Appalachian states, The information should prove valuable not only to the coal industry but also to industry in general as a means of evaluating both pollution control action that has been taken to date and the course of future control measures. Reference information in the forms of addresses of appropriate agencies and citations to specific state laws and regulations is provided. All information is current as of February, 1969.

Jan 1, 1969

By R. W. Heckel, R. A. Tanzilli

Treatment of the finite, diffusion-controlled, two-phase, moving-interface homogenization problem has been carried out by numerical methods for a wide range of input parameters. Solutions have been obtained for planar, cylindrical, and spherical diffusion geometries. The effects of parameters such as the interdiffusion coefficients (concentration-independent) of- both phases, the concentrations (time-independent) of each phase at the interlace, mean composition, initial size of the dissolving- phase, and initial composition of- the two phases are considered. The results are displayed to show both the position of the interjace and the degree of homogenization (expressed in terms of concentration at the matrix phase symmetry boundary) as a function of diffusion time. Typical exaw~ples to which the results may be applied are discussed. A limited number of exact, closed-form solutions to the multiphase, diffusion-controlled, moving-interface problem exists in the literature, e.g., Refs. 1 to 7. The exact, closed-form solutions generally consider the outermost phases to be infinite in extent and also assume an interfacial velocity function. It is through use of such boundary conditions that closed-form solutions are readily obtained. An extensive literature also exists on numerical solutions to the mathematically analogous solidification problem, e.g., Refs. 8 to 12. In addition, a numerical solution involving mass transfer with spherical interfaces and infinite boundaries has recently been carried out.13 A practically important class of diffusion problems exists, however, in which the boundaries of each phase away from the interface are finite. For example the finite boundary condition arises when one sets up a model for analyzing the homogenization behavior of two-component powder compacts in two-phase systems or for studying the solution behavior of precipitates. Although exact, closed-form solutions have as yet not been found to this class of problems, solutions are possible using numerical methods. The purpose of this paper is twofold: 1) to describe a numerical method for treating the two-phase, diffusion-controlled, moving-interface problem involving finite boundaries with planar, cylindrical, and spherical interfaces; 2) to present the results of a parametric study which identifies the role played by each variable appearing in the analytical model. R. A. TANZlLLI,Student MemberAIME,onleaveofabsence from the General Electric Co., Re-entry Systems Department and A. W. HECKEL, Member AIME, are Graduate Student in Materials Engineering, and Professor, Department of Metallurgical Engineering, respectively, Drexel Institute of Technology, Philadelphia, Pa. Manuscript submitted May 6. 1968. IMD MATHEMATICAL MODEL The three geometries analyzed are shown in Fig. 1. For each configuration a symmetry element is shown, across whose boundaries the mass transfer is zero. Mean composition, C, and the characteristic solute-rich phase half-thickness (or radius), 1/2, are the independent variables while the characteristic symmetry element half-thickness, L/2 (measured from solute-rich phase center to the matrix phase plane of zero mass transfer), is a dependent variable. The symmetry element for a planar interface accurately represents a real diffusion situation involving the stacking of symmetry elements of constant size. Because cylindrical and spherical symmetry elements of constant size cannot be stacked to fill space, the meaning of the dimension, L/2, for these situations may be considered in terms of the following approximations: and where NA is the number of parallel cylindrical elements per unit area on a surface normal to the cylinder axes and Nv is the number of spherical elements per unit volume. The model consists of a solute-rich phase matrix phase composite of limited mutual solubility. The concentrations at the interface are assumed constant with time; no assumption of local equilibrium at the interface is necessary except for the case where the

Jan 1, 1969

By N. A. D. Parlee, I. D. Shah

THIS communication reports the results of some work done on the effect of gold, palladium, and platinum on the liquid-gas-solid equilibrium in the Ag-O system,1,2 see Fig. 1. Recently several investigators3, 4, 5 have reported the effects of gold, palladium, platinum, and copper on the solubility of oxygen in liquid silver. This communication represents only a portion of the work done here on the solubility of oxygen in liquid silver and liquid Ag-Au, Ag-Pd, and Ag-Pt alloyss—the greater part having already been reprted. The apparatus, materials, and procedures used were similar to those of earlier work.&apos; l The main precautions observed in obtaining these freezing points at constant temperature and PO2 = 1 atm were as follows: 1) The points were approached very slowly from higher temperatures. 2) In the very near vicinity of the L-G-S equilibrium point precautions were taken to see that the melt was in equilibrium with oxygen at one atm. Equilibrium was considered to have been attained when no more absorption of oxygen was observed in the last 15 min at a fixed temperature. 3) In the case of these alloys, the freezing point of the melt at 1 atm of oxygen and the equilibrium amount of oxygen absorbed by the liquid "infinitesimally" above this point were determined by lowering the temperature in very, very small steps, equilibrating at

Jan 1, 1969

By V. F. Swanson

A petrographic study was made of the type and sources of mineral contamination occurring on phosphate rock products from Florida. Emphasis was placed on contaminants in the screened rock (+1 mm) since this portion of the product undergoes no physical beneficiation except for scrubbing to remove slimes. Since iron and aluminum con- tent of the finished product affect the salability, special emphasis was placed on identifying types and sources of these contaminants and relating chemical composition to visual characteristics. Wavellite derived from the overburden was the major aluminum contaminant with some aluminum being included as secondary clayballs. Iron occurred as phosphates in the overburden, and as colloidal oxides included in the phosphate pebbles. Chert and limestone contamination were derived from the Hawthorne formation underlying the phosphate matrix.

Jan 1, 1969

By Thys B. Johnson

Traditional mine planning concepts are discussed and suggestions for improvement through use of the developed model are proposed. The approach developed in this paper allows optimal planning of the complete mining-concentrating-refining system over the entire planning horizon and permits the system to dictate how and when to process a block of material, i. e., a dynamic cutoff.

Jan 1, 1969

By D. L. Babbitt, Sniezek

"This paper deals with the varions methods for the rapid Joading of unit trains which are being: used by ore procossors to move their product to dock-s1de storage facilities or their ultimate customer. Some of the techniques that have been used include (1) volumetrie loading, both in motion and static, (2) batch weighing into moving cars and (3) batch weighing into cars that have been stopped. Particular emphasis shall be placed on the two systems now in use at the Adams Mine facility of Jones and Laughlin Steel Corporation and at Cliffs of Canada's Sherman Mine. Typical ""turnaround"" times, loading rates, types of cars, weighing accuracies, material handling concepts and maintenance considerations shall be discussed."

Jan 1, 1969

By John L. Halls

Modern business practice dictates that in order to ensure the economic optimization of investment, the size of any investment venture must be such that every increment of capital invested in such a venture yields at least a corporate minimum acceptable rate of return. This practice is based on the premise that alternative investment opportunities capable of yielding the minimum corporate return are immediately available. If a mining corporation is to make the maximum use of its investment funds, any capital investment in a mining property must comply with the above practice. The most important parameter in estimating ore reserves is the cut-off grade which is used to separate material into ore or waste. The cut-off grade is calculated on the basis that material of cut-off grade produces sufficient revenue to cover the estimated costs of mining and processing through to sales, including depreciation and produce a pre-determined profit. Ore reserves so estimated are adequate for determining the magnitude of an orebody but do not provide a sound basis for determining plant size and therefore capital investment in a new property or for expansion consideration on an existing property. From a financial analysis of this one ore reserve it is impossible to ascertain whether each increment of capital investment is providing the minimum acceptable rate of return, Other difficulties associated with the calculation of a cut-off grade including the determination of depreciation and the amount of pre-determined profit to be included in the cut-off grade calculation are outlined in the text. The proposed solution to determine optimum ore reserves and plant size for new properties avoids the complication of calculating a cut-off grade by computing a series of ore inventories using arbitrarily selected cut-off grades. A comparison of the cash flows generated by production from such ore inventories using incremental financial analysis clearly indicates the ore reserve and plant size which will best serve the corporation&apos;s investment and metal production goals. Incremental financial analysis of a corporation&apos;s operating mines and prospects assists management in assessing the comparative expansion and investment possibilities of each property for increasing or maintaining metal production on a long term basis.

Jan 1, 1969

By J. L. LeBlanc, R. L. Lewis

This study presents an analysis of annular backpressure variations associated with controlled gas kicks and their pronounced effect on casing .strings and exposed under lying formations. A mathematical model describing the volumetric behavior of an extraneous gas as it is transported from reservoir to .surface conditions under changing temperatures and pressures has been programmed in a Kingston FORTRAN II language for digital computer analysis. The gases under investigation typify Gulf Coast reservoir gases within a 0.6 to 0.7 .specific gravity range. The program output has been substantiated by actual field cases. of gas kicks encountered in Gulf Coart we1l.s. The development of empirical equations for calculating suitable gamy deviation factors for unique temperatures and pressures was incorporated in the program to provide realistic solution.. An output listing of annular backpressures and corresponding equivalent fluid densities resulting at a predetermined critical depth (casing setting depth) and total depth for selected .stages of circulation is provided in a chronological .sequence. Additional information including reservoir pressure and temperature, kill rnrid density, produced gas or surface volume of the expanded gas intro vion, drill pipe and annular volumes can he obtained from the model. This paper illustrates that a precise knowledge of the volumetric behavior of extraneous gases in annular flow and its effect on equivalent fluid densities at a critical depth is significant and should receive .serious consideration in controlling threatened blowouts and in the design of drilling programs. Surface pressures in excess of formation limitations are a threat to zones of lost circula/ion and are potentially injurious to productive intervals. A knowledge of annular backpressure and equivalent fluid density profiles for probable gas kicks aids in a technological accomplishment of drilling programs and provides a .sale tolerance in the event a threatened blowout is encountered. Introduction Drilling operations are frequently interrupted when the drill bit penetrates permeable gas sands with reservoir CtfuJ manuscript was received in Society of Petroleum Engineers ofice Am. 1 1967. Revised manuscript received JuIy 7. 1968. Paper (SPE 1860) kae presented at SPE 42nd Annual Fall Meeting held in Houston. Tex., Oct 1-4, 1967. @ Copyright 1968 American Institute of Mining, Metallurgical, and Petroleum Engineem, Inc. pressures greater than that exerted by the drilling fluid. The differential pressures resulting permit an extraneous influx of gas into the wellbore. A suspension in drilling progress is necessary to restore fluid equilibrium throughout the system. Whether formation gas kicks originate unintentionally or by design, the prospect of a threatened or actual blowout exists and a method assuring a safe and effective well control procedure must be observed. A significant contribution to well control technology was advanced by Records et a1.l in 1962. Using the concept of transmitting a constant equivalent formation pressure at the point of intrusion, Records et al. introduced a calculation technique providing the annular backpressures encountered in a well control environment as a func tion of the volumetric behavior of a 0.6 specific gravity natural gas. In essence, the procedure outlined an annular backpressure schedule in terms of fluid volume circulated at different stages of a well control operation. A number of other publications2-&apos; proposing various techniques for controlling gas intrusions in a wellbore achieve pressure control essentially through maintenance of a constant bottom-hole pressure by surface choke adjustments. The subsequent pressure effects induced in the annulus unfortunately receive little emphasis. Due to the tedious and repetitive nature of annular backpressure computations, a theoretical solution by digital computer is introduced for predicting annular backpressure and equivalent fluid density profiles associated with controlled gas kicks. We point out the effects of volumetric behavior of extraneous gases in annular flow and related field phenomena on equivalent fluid densities at a critical depth. The investigation indicated that equivalent fluid densities at a critical depth are of significance and should receive consideration in the control of threatened blowouts and in the design of drilling programs. Theoretical Considerations The mechanism of vertical gas flow through an annulus is governed by the PVT properties of the fluid, the pressure distribution within the system, the fluid flow rates and the geometry of flow. Due to the numerous variables involved in this type of problem, certain assumptions were imposed in deriving the mathematical model and in establishing the solutions. Two gases, characterized by specific gravities of 0.6 and 0.7, were selected to typify Gulf Coast reservoir fluids. The gas intrustion entered the wellbore as an immiscible &apos;References given at end of paper. JOURNAL OF PETROLEUM TECHNOLOGY

Jan 1, 1969

By C. F. Cockrell, H. E. Shafer, J. W. Leonard

A significant technological development is discussed for the processing of certain power plant flyashes that are a problem because they contain a high water-soluble mineral content and yield inferior flyash-based brick. This development is based on the addition of hydrochloric acid to the flyash-bottom ash-sodium silicate blends used for the production of flyash-based structures. Favorable changes are evi-dent in sodium silicate consumption, where about half the amount used for making brick from normal flyash is required, processing costs, and strength and appearance of the resulting freshly formed green and fired structural products. In some high cost in-stances (above the $30 or less per thousand brick estimated for normal flyash), hydrochloric acid additions can replace or reduce other costly additives normally required for problem flyashes. This results in savings of as much as $9 per thousand brick. These developments offer promising possibilities for utilizing problem flyashes as well as flyashes which may come into contact with water soluble sulfur as a result of the eventual application of certain experimental air pollution control processes. Much of the research datal-6 accrued through work by the Coal Research Bureau of West Virginia University for the Department of Interior&apos;s Office of Coal Research on converting waste power coal ash to valuable brick and other structural products, can be categorized as follows: (1) general ash-to-brick tech- nology; (2) specific ash-to-brick optimization; (3) pilot plant progress; (4) production cost estimates. A summary of the progress on bench-scale experiments indicates that coal ash can yield two types of brick. An acceptable brick is obtained by mixing 73.6% fly-ash, 23.5% bottom ash and 2.9% sodium silicate solution (dry basis). Depending on the flyash and bottom ash used, optimum brick can be manufactured by mixing 72-77% flyash, 20-25% bottom ash and 2.3-3.0% sodium silicate (dry basis) with Na2O : SiO2 ratio varied according to the composition of the flyash used. These blends are thoroughly mixed and mechanically formed into green brick shapes at pressures ranging from 1000 to the more usual 3000 lb per sq in. The green shapes then are dried and fired at temperatures ranging from 1975-2150°F using clay brick cycles that are shorter than standard. Other findings reported to date indicate that when making optimum brick, it is necessary to carefully control the top size of the moisture-releasing bottom ash so that it falls between 8 and 30 mesh, depending on the flyash used. Moreover, the chemical composition of bottom ash and flyash have been found to be of little significance with the exception of a few problem flyashes which are the subject of this paper. Finally, the pilot plant, which was previously reported under construction, is now in operation. This will indicate, among other things, the cost of brick production, which was earlier estimated for non-problem flyashes at $30 or less per thousand brick. The foregoing bench-scale technology is applicable to all the initially tested ashes as well as to the majority of ashes examined during the course of research. However, a few of the ashes yield green and fired products that may be structurally inferior or unacceptable, necessitating excessive and diverse reagent addition, and/or may be coated with unsightly surface deposits. These problem ashes generally originate in certain areas of Illinois, western Ken-

Jan 1, 1969

By R. J. Burgess, A. R. Ramey, A. R. Adams

During interpretation of pressure buildup tests on gas wells in a tight dolomite gas reservoir, peculiar behavior was noticed. Two straight lines were apparent. Effective permeability to gas taken from either straight line was about the same, and the Miller-Dyes-Hutchinson dimensionless time check for the straight line was proper for both straight lines. Geological data indicated the likelihood of scattered trending fractures in the reservoirs. Since the first straight Iine yielded permeability values close to the geometric mean permeability from core analyses, it was postulated that the reservoir model was that of an acidized well completed in the tight dolomite, but that widely scattered hairline fractures caused the mean permeability of the reservoir distant from the well to be higher than the matrix permeability. Because all other studies of fractured reservoirs to the authors&apos; knowledge assumed that the fracture matrix was dense enough to communicate directly with the well, no interpretative methods were available. The Hurst line-source solution for a radial change in permeability for interference between oil reservoirs was adapted to pressure buildup testing. The result indicated that the first straight line should yield the proper matrix permeability and wellbore skin effect. The second straight line may be extrapolated to obtain static pressure. The time of bend between the straight lines was used to estimate distance to a fracture. Application to field test data is shown. It is believed that the methods developed and the case history presented will add to present tools available for pressure buildup interpretation. Introduction Since the pioneer studies by Miller, Dyes, and Hutchin-son1 and Horner&apos; in 1950 and 1951, well test analysis has become recognized as one of the most powerful tools available to both production and reservoir engineers. Well test analysis serves as a logical basis for well stimulation and completion analysis, and for long-term reservoir engineering. Since the early 19501s, much effort has been placed on the development of well-test analytical methods. Reservoir and well conditions of increasing complexity have been considered systematically to provide the analyst with a catalog of causes and effects. Matthews and Russella state that some 200 papers dealing with this subject have been published in the last 35 years. Developments in well test analysis appear to have originated in one of two ways. Either a physically realistic field condition was anticipated and analytical solutions for the condition achieved, or anomalous field test behavior was recognized and interpretative methods sought for the anomaly. In recent years, it has appeared that the latter has inspired an increasing number of studies. The analyst today finds an increasing number of known cause and effect studies available for well test analysis, the classic of which is that of finding the specific flow problem that generated the answer — the well behavior. Although it may be impossible to achieve this goal uniquely, the analyst often is able to select a useful interpretation that combines all known performance and geologic data — or to show that various logical alternatives would not significantly affect the interpretation. During a recent reservoir study, we observed gas well test behavior that did not appear to fit behavior described previously. Although it cannot be said that we have found a unique interpretation, we shall present in this paper the peculiar behavior observed, and describe the reservoir and interpretative methods developed. Reservoir Description The subject gas reservoir is a 9-mile-long, narrow dolomite reservoir lying within a limestone of Ordovician age. (See Fig. 1.) The dolomitized rock in the field consists of dark brown to buff, dense to coarsely crystalline, vugular dolomite containing numerous hairline fractures, many of which may have been closed in the reservoir and parted when cores were brought to the surface. Larger fractures are also apparent in core, but usually are filled and sealed with euhedral dolomite crystals. Portions of the north flank of the reservoir are known to be cut by a sealing fault downthrown to the north. Gas wells located near the fault have higher open flow potentials than those more distant from the fault. This is believed to be a result of higher permeability near the fault due to more extensive and open fractures. Detailed coring and core analysis have been performed on several of the wells in this reservoir. Fig. 2 presents permeability variation&apos; plots for both horizontal and vertical

Jan 1, 1969

By Frank C. Schora

The Institute of Gas Technology for many years has dedicated a large portion of its research effort to the development of a practical solid-fuel-based gasification process to produce a synthetic natural gas equivalent. The work is being done to prepare for the day when supplemental gas will be needed. This program, initially supported by the American Gas Association, and now by both the Department of Interior&apos;s Office of Coal Research and the American Gas Association, has developed the IGT Hydrogasification Process. This process, now entering the pilot plant stage, is based on the high-temperature, high- pressure hydrogenation of coal with a hydrogen-steam bearing gas. Product gas from this step is cleaned and catalytically methanated to produce a high-Btu gas. Estimated production costs indicate the process will be competitive with natural gas in certain areas of the country when required.

Jan 1, 1969

By H. T. Shore, J. M. Schultz

A number of experimental rnethods—X-ray powder diffractometry, Laue photography, X-ray small-angle scattering, and transmission electron microscopy and dijfraction—have been utilized to examine the morphology associated with precipitation from the terminal, g, solid solution of a Zn-1 pct Cu alloy. A significant age hardening was observed in a 1 pct Cu alloy. X-ray and electron diffraction results showed that the structural inhomogeneities associated with the hardening were isotructural with the matrix. The average size and shape of the inhomogeneities were deduced from the electron microscopy and X-ray small-angle scattering. The preprecipitates are hexagonal platelets some 300? in diam. and some twelve unit cells thick. The orientation of the platelets was deduced from Laue photographs and electron diffraction. The platelet plane is (0001). When a large amount of pre-precipitation is present in a localized volume the new lattice is often disoriented by a rotation about (0001) of of the matrix. WhILE dilute Zn-Cu alloys have been commercially important for some 50 years, relatively very little is known metallographically about this material. The "Zilloys", zinc with about 1 wt pct Cu and sometimes a small addition of magnesium, are used to produce rolled zinc which is harder and stronger than that produced by other rollable zinc alloys.&apos; According to the phase diagrams of the zinc-rich side of the Cu-Zn system, such dilute Zn-Cu alloys should age-harden;2-5 the solubility of copper in zinc, g-phase, at 424°C is 2.68 pct, while at 0°C it is only to 0.3 pct. However, the published literature on the aging of this system appears to be limited to a documentation of the contraction of 1, 2, and 3 pct Cu alloys aging at 95°c,6 and an attempt to measure changes in lattice parameters during aging.&apos; In the latter work, no lattice parameter changes were detected, although a broadening of the highest-angle lines was detected and considerable diffuse scattering was observed. Micro-structural investigations have been limited to the latest stage of aging, wherein Widmanstatten precipitates are formed.3,47 These alloys are of interest for still another reason. The two most zinc-rich phases in the Cu-Zn system, 77 and E, are both hcp. Moreover, the change in a, between 17 and t for a 1 wt pct Cu alloy is onlv 3.64 -,~ct: the change in Co is 12.0 ict. It would be anticipated that precipitation in such a material might occur through metastable phases or G.P. zones with epitaxy along mutual 0001 planes. The goals of the present work are aimed at partially filling the void of knowledge concerning the early stages of precipitation from the g phase. In particular, we have attempted to document the magnitude of the age hardening of this system and to determine the size, shape, and orientation within the matrix of the elements of precipitation in an early stage of condensation. EXPERIMENTAL A) Specimen Preparation. Specimens were prepared In two somewhat different ways, one method being used for X-ray Laue and diffractometer measurements, optical microscopy, and Rockwell hardness measurements and the other used for electron microscopy and X-ray small-angle scattering. In the first case zinc and copper in the proper proportions to yield a 1 wt pct Cu alloy were melted together in a closed graphite crucible. Castings so made were free of apparent segregation or oxidation. The castings were then solution-annealed at 400°C for several days and then quenched in water to room temperature. Filings of portions of the specimens were made for use as X-ray powder diffractometry specimens. The electron microscope material was made as follows. Castings were made under vacuum with copper powder placed inside a hollow zinc cylinder to insure good contact of the materials. These 1 wt pct Cu pieces were then rolled to 0.1 mm with an intermediate anneal in vacuo. The rolled sheets so formed were then annealed for about 6 hr at 225°C. Finally the specimens were electropolished slowly until thin enough for transmission electron microscopy. The polishing is discussed in greater detail in the Results section. B) Measurements. X-ray measurements of three types were performed. A G.E. XRD-5 diffractometer was used to examine powders of the alloy for identification of second-phase material. A Kratky small-angle camera, also operating from a G.E. tube, was used to investigate the sizes of small precipitate particles. In both cases, nickel-filtered copper radiation was utilized. Finally, individual grains of the large-grained castings were examined in the back-reflection Laue geometry. Electron microscope studies were carried out with a J.E.O.L. Model 6A instrument. RESULTS A) Hardness Measurements. Hardness measurements performed at room temperature on the large-grained polycrystalline specimens showed a hardening which was essentially complete in 3 hr. Fig. 1 shows a typical plot of hardness vs aging time. The relative magnitude of the ultimate hardening varied from run to run between 150 and 200 pct of the value for the material immediately after quenching from the solution anneal. Most probably the variations reflect small changes in the time taken to remove the specimen from the vacuum furnace after the solution anneal.

Jan 1, 1969

By J. M. Oblak, W. A. Owczarski

A cellular appearing recrystallization product formed by annealing a cold-worked nickel-base super-alloy at 1800°F has been studied by electron nzicroscopy. Prior to deformation, an equilibrium micro-structure of fcc matrix y and cuboidal ,,&apos;, Ni (Al, Ti), precipitates of CuzAu structure had been established by an age at 1825°F. The strain-free recrystallization cells consist of very large rodular y&apos; particles in a y matrix. They precipitate is oriented and coherent both before and after recrystallization. The results showed that y&apos; coarsening accompanies recrystallization at 1800°F. However, it does so as a secondary effect and does not necessarily take place at lower temperatures. The structural similarity of this reaction to cellular precipitation in other systems indicates that lattice strain may also play a significant role during some cellular precipitation reactions. THERE have been numerous microstructural investigations of recrystallization in single-phase materials but two-phase systems have received much less attention. The second phase can either remain inert or be altered along with the matrix during recrystallization. If the second phase is an oxidelm3 or a relatively inert pre~ipitate,~, recrystallization is retarded when the interparticle spacing is less than 1 p. Prior to the onset of recrystallization, these materials show a well-polygonized substructure with the subgrain size limited by the interparticle spacing. Since recrystallization by the motion of preexisting grain boundaries6 is not observed, retardation has been related to particle pinning of the subboundaries. This pinning prevents coalescence&apos; or growth8 of subgrains to a critical size (formation of a high-angle boundary) necessary to initiate recrystallization. In a material such as a nickel-base superalloy both y matrix and y&apos; precipitate are altered by the recrystallization reaction. Haessner et al.&apos; studied the recrystallization of a cold-rolled Ni-Cr-A1 alloy by electron microscopy. The material was initially cold-rolled in the supersaturated condition. upon annealing at 750°C, immediate precipitation of 7&apos;occurred. Presence of this 7&apos; greatly retarded the onset of recrystallization which eventually took place by the development of randomly oriented, strain-free grains. The original •/ was dissolved at the recrystallization interface and reprecipitated as oriented, coherent par-tiles in the new grain. Recrystallization caused a refinement of .)&apos; particle size. Recently ~hillips&apos;&apos; investigated recrystallization of Ni-12.7 at. pct Al. Reduction by cold rolling presumably elongated the p&apos; precipitate into lamellae that remained coherent with the matrix. After recrystallization at 600" to 750°C, there was no unusual change in y&apos; particle size al- though there was a tendency toward clustering along the prior rolling direction at 750°C. Above 750°C, the recrystallized grains were generally free of precipitate. Studies in the somewhat analogous Cu-3.23 wt pct CO" and Cu-2 wt pct&apos;2 systems demonstrated that the coherent cobalt-rich fcc precipitate in these alloys obstructed softening, initiation, and completion of recrystallization. The precipitates were deformed into lam~llae during rolling and those of diameter less than 250A remained coherent. Recrystallization took place by the growth of new grains into the recovered or poly-gonized material. In the first study," both matrix and precipitate reoriented in the same manner upon passage of the recrystallization interface. There was no change in particle size or morphology. Tanner and ~ervi,~ on the other hand, observed that motion of the recrystallization fronts was strongly hindered by the pinning action of coherent precipitates in the deformed material. Particles in contact with a pinned boundary coarsened and coalesced leaving a denuded zone in the unrecrystallized region. When the number of pinning points was sufficiently reduced by coalescence, the boundary swept past these particles and through the denuded zone. The authors1&apos; considered this as a variation of discontinuous precipitation with both chemical driving force and deformation strain energy contributing to recrystallization. Preliminary observations by the present authors had revealed that recrystallization in Udimet 700, a nickel-base superalloy, occurred in an entirely different manner. Optical metallography showed that the recrystallized product formed as cellular colonies containing coarse y&apos; particles elongated in the direction of cell growth. In this investigation the structural features of this reaction were investigated by transmission electron microscopy. EXPERIMENTAL PROCEDURE As-received I$-in. rounds of Udimet 700* were (wtpct) 18.4 15.2 4.95 4.42 3.43 0.06 0.031 0.14 Bal. solution-annealed for 4 hr at 2150" and then fast air-cooled. An initial y-~&apos; structure was established by a 4-hr age at 1825°F followed by a fast air,cool. Essentially the equilibrium volume fraction of ?&apos; at 1825°F is precipitated within 4 hr. Microstructural examination showed no measurable increase in the amount of precipitate after longer aging times. Deformation consisted of swaging to 52 pct RA with 6 pct reduction per pass at room temperature. To reduce the precipitation potential to a negligible amount, recrystallization anneals were conducted at 1800"~ (982"~). Microstructures were investigated by optical and transmission electron microscopy. To prepare foils for electron microscopy, the material was first sliced into 30-mil slabs parallel to the swaging direction. Discs were dimpled and electrolytically cut from

Jan 1, 1969

By R. A. MacGregor

The Stanreck mine of Stanreck Uranium Mines Limited in located on Quirks Lake in the Elliot lake - Blind River area of Northern Ontario. It is approximately 25 miles north of the north shore of Lake Huron, equidistant between the cities of Sudbury and Sault Ste. Marie. The property was developed ad brought into production at a rate of 3,000 tens of ore/day during the uranium boom of the mid 1950&apos;s. By 1960 mine waters were becoming quite acid through the activity of bacteria. Treatment of this water was begun for pollution control and a small amount of uranium which had been leached from the ore by these acid waters was recovered. Development of bacterial leaching with a view to increasing production by this method commenced in December 1962. Subsequently, it was succeesfull in producing 10,000 - 15,000 lbs. of U308/month. Since late 1964 uranium production has been obtained solely from bacterial leaching. A rare earth concentrate was also made for its yttrium content during 1966 and 1967. This paper describes the development, operation and methods used in the underground bacterial leaching process.

Jan 1, 1969