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By W. S. Hyler, L. W. Berger, R. I. Jaffee

Hydrogen additions of 390 ppm to A-55 titanium and 368 ppm to Ti-8 pet Mn have no deleterious Hydrogenadditionseffect on the unnotched and notched rotating-beam fatigue properties of these materials. 'These amounts of hydrogen, however, are sufficient to cause severe notch-impact thesematerials.embrittlement in A-55 titanium and pronounced loss of tensile ductility in Ti-8 pet Mn. The lack of embrittling effect in fatigue in the latter alloy is consistent with the postulated strain-aging mechanism of hydrogen embrittlement in a-ß alloys. There is a significant strain-agingincrease in the unnotched endurance limit of A-55 titanium with the addition of hydrogen. This increase may be explained as the result of internal heating effects which would dissolve the hydride and cause solid-solution strengthening. TITANIUM and its alloys may be seriously embrittled by relatively small amounts of hydrogen. The form which this embrittlement takes has been shown to vary with alloy type. The a alloys, for example, suffer most strongly from loss of notch-bend impact toughness' when sufficient hydrogen is added, and this effect has generally been associated with the presence of hydride phase in the micro-structure. In a-ß alloys, on the other hand, hydrogen is most detrimental to tensile ductility in slow-speed tests,2-1 and the embrittlement may be detected in a most convincing manner by means of rupture tests at room temperature. This particular kind of embrittlement has not been associated with a change in microstructure, but has been classified rather generally as associated with a strain-aging type of mechanism.' In the present paper, the effect of an embrittling amount of hydrogen on the rotating-beam fatigue properties of both an a and an a-ß titanium alloy is covered. For this study, annealed commercially pure (A-55) titanium was chosen as an a alloy, and equilibrated and stabilized Ti-8 pet Mn as representative of a typical a-ß alloy. Nominal hydrogen levels of 20 and 400 ppm were evaluated, the latter amount having been shown previously to be severely detrimental to the impact toughness of commercially pure titanium and to cause pronounced strain-aging embrittlement in the Ti-8 pet Mn alloy. The only report of the effect of hydrogen on the fatigue properties of titanium is given by Anderson et al.,° in which a push-pull type of fatigue test was conducted on as-received commercial-purity titanium sheet. Much scatter was found in the results, but generally the presence of hydrides slightly decreased the fatigue strength of unnotched specimens in the longitudinal direction. The results of notched tests were masked too greatly by scatter to be significant. Experimental Procedure Preparation of Materials—Analyses of the A-55 titanium and the Ti-8 pet Mn alloy used in this investigation are given in Table I, which indicates the 8 pet Mn alloy to be more nearly a 6 pet Mn alloy. This alloy will be referred to as Ti-8 pet Mn, however, since this is the commercially designated composition. Both alloys were received in the form of5/8-in. diam rod and, after suitable surface preparation, 5-in. lengths were vacuum annealed at 820°C. Half of the rods for each material were then hydrogenated at 820°C to a nominal hydrogen content of 400 ppm. The hydrogenated and vacuum-annealed A-55 rods were hot swaged at 700°C from 5/8-in. diam to 1/4-in. diam, and then annealed 1 hr at 800°C and air cooled prior to preparation into test specimens. Fabrication of the Ti-8 pet Mn alloy was by hot swaging to 3/8-in. diam at 760" and then 1/4-in. diam at 704°C. This material was then annealed 1 hr at 704", followed by furnace cooling to 593"C, and finally air cooling to room temperature. Evaluation—In order to examine more completely the effects of hydrogen on the particular materials studied, slow-speed tensile and notch-bend impact properties were determined in addition to fatigue data. Tensile specimens were of the standard ASTM type with a reduced section of 1/8-in. diam and a gage length of 1/2 in. A subsize cylindrical Izod specimen was used for impact tests. These specimens had a 45" notch with a 0.005-in. radius and a 0.150-in. root diam, and the stress concentration factor of this notch in bending was Kr = 3. Both the ten-

Jan 1, 1959

By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of 'irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.' beryllium,' magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.' A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967

By G. R. Speich, D. J. Mack

The transformation of was studied by isothermal methods. At all temperatures, the ß transforms quickly to fine grained ß" which develops silver-rich striations. At higher temperatures the striations disappear, the final structure being Widmanstatten a in ß'. At lower temperatures, the striated ß" is consumed by pearlite nodules of a + ß' which in turn form the Widmanstatten a in ß'. The transformation is unlike any previously reported for a eutectoid. AS part of a general program of study on the eutectoid reaction, the Ag-Cd eutectoid seemed particularly attractive because the ß phase which undergoes the reaction is another of the typical "electron compounds," AgCd, having the disordered body-centered cubic structure. This work deals with the eutectoid which occurs at 50.5 wt pct Ag, and not with the eutectoid which has been reported at 42.9 pct Ag.' There has been no work reported specifically on the Ag-Cd eutectoid which was studied. The only information available on this eutectoid is that work done in the determination of the phase diagram. For the most part, the terminal portions of the diagram, Fig. 1, are well established; however, the region from 40 to 60 pct Cd is still somewhat in doubt. The X-ray evidence'..' in this region is in conflict with the results of thermal analysis. X-ray analysis3 does not show a polymorphic transformation at about 240°C as indicated by thermal analysis.1,5 Even the X-ray evidence, within itself, is confusing in this region of the diagram. One investigator2 reports the ß phase as hexagonal close-packed and has found three phases in the one-phase ß field. Other X-ray investigators"' ' report the ß phase as body-centered cubic. The authors believe that much of the confusion resulted from incomplete homogenization of the alloys. It was found that it takes almost a week to produce a completely homogeneous two-phase structure at 370°C. Another possible source of error is the volatilization of cadmium from the surface and cracks of the specimen during annealing with the possible formation of a cadmium-poor phase. The only metallographic data available on this eutectoid alloy are those of Durrant1 and Fraenkel and Wolff.5 his information is very limited. The phase diagram chosen as most nearly correct is that in the Metals Handbook," which is almost identical with the phase diagram suggested by Durrant.1 Materials and Procedure The alloy was prepared from high purity silver (999.5 plus fine) and high purity cadmium (0.02 Pb, 0.005 Cu, trace Fe). The metals were melted in carbon under a nitrogen atmosphere. Some cadmium was lost by volatilization but by remelting several times and adding cadmium a 200 g ingot of approximately eutectoid composition was obtained. Because the CdO fumes are quite toxic, the exit gas from the furnace was led through a water trap to condense the CdO. The ingot was homogenized at 650°C for 24 hr, no attempt was made to prevent decadmiumization. This resulted in a narrow decadmiumized rim on the ingot which was removed. Filings for analysis were obtained from cross sections of the ingot. Silver was determined by the Volhard thiocyanate method,? cadmium by difference. The ingot analyzed 50.8 pct Ag at the top of the ingot and 50.7 pct at the middle and at the bottom of the ingot. This alloy was only slightly hypo-eutectoid compared to the accepted value of 50.5 pct Ag and was used for the isothermal studies. It was felt that further attempts to adjust the composition might be futile because of the volatility of the cadmium. The ingot was sectioned to specimens approximately 3/4 x 3/4 x 1/8 in. These specimens were "austeni-tized" for 3 hr in air at 650°C to yield homogeneous ß and then quenched into a salt bath held at constant subeutectoid temperatures where the transformation

Jan 1, 1954

By O. D. Gaither

This paper is an analytical study of the flow of fluids through small vertical conduits. Small conduits are defined as 11/4-in. nominal diameter tubing size and smaller, and approximately twice this area for annular conduits (i.e., 1- X 21/2-in. annulus and smaller). Experimental data are presented for the 1-X2-in. and 11/4- X 2%-in. annuli, and the I-in. and 11/4-in. tubing, since these represent the small conduit sizes and configurations generally encountered in oilfield applications. Data have been gathered for these conduits for single-phase water, single-phase gas and two-phase water-gas mixtures, with particular emphasis on high gas-liquid ratios. Water rates in excess of 2,000 BID and gas rates in excess of 2.5 MMcf/D, and two-phase flow ratios in between these two, represent the scope of the data gathered. Existing equations have been applied to predict flowing pressures and compared with experimental data. New correlations have been developed. INTRODUCTION The increased economic pressure on the domestic oil industry in the United States has constantly required the use of new techniques and equipment designed to reduce the cost of finding and producing oil and gas. Since tangible items are most readily apparent in economic analysis, the advent of lower-cost well completions was inevitable. One of the methods used to reduce costs which has received widespread attention is the slim-hole completion technique where tubing is used as the well casing and in which small conduits are used for tubing if necessary. Small conduits, defined by Kirkpatrick1 as "11/4-in. diameter nominal tubing and smaller for tubing flow and less than twice the 11/4-in. diameter nominal tubing internal flow area for annulus flow", have also found widespread usage as siphon strings for de-watering gas wells and as "kill" strings in deep high-pressure oil and gas wells. The growing use of small-diameter tubing has resulted in an increased need for development of improved methods to measure or predict flowing bottom-hole pressures since the physical dimensions generally preclude the use of subsurface-recording pressure gauges. Even in the cases where small bombs are available, the relatively high velocities encountered at nominal flow rates make it necessary to use excessive weight bars or special hold-down devices. Attempts to use recognized correlations to accurately predict flowing or gas-lift performance in wells equipped with small conduits have been generally unsuccessful. Insufficient field data were available to allow the development of a correlation on this basis, and an experimental approach was applied in an attempt to obtain a workable relation. The experimental approach used to obtain the data presented in this paper was actually a compromise between a field installation and a laboratory study. A test well 1,000 ft in length was used to obtain flow data on single-phase liquid, single-phase gas and two-phase water-gas flowing mixtures. Liquid rates up to 2,200 B/D and gas rates up to 3 MMcf/D were used in the single-phase flow studies. Two-phase flow rates from 100 to 600 B/D with gas-liquid ratios from 500 to 8,000 cu ft/bbl were recorded. Experimental data were obtained for single- and two-phase flow through 1-in and 11/4-in. nominal tubing, and through the annuli between 1- and 2-in. and 11/4- and 2%-in. nominal tubing strings. Experimental results for the two-phase flow are compared to the Poettmann-Carpenter correlation2 which is widely used as a comparative standard for development of multiphase flow predictions in flowing and gas-lift wells. Correlations developed by Tek,3 Baxendell and Thomas" were also investigated. The experimental data recorded herein fell in between the two flow regimes as defined by Ros," and this correlation also failed to yield satisfactory results. The fact that existing correlations failed to confirm the experimental data led to the need for development of a new correlation. Although a two-phase flow study was the primary objective of this investigation, data were also recorded for single-phase flow of water and gas, and constants were developed relating to pipe roughness and equivalent diameters for annular flow. These single-phase studies assisted materially in the development of certain of the two-phase flow results. Considerable previous work has been published which presented relationship of surface measurements to bottom-hole condition. The works of Buthod and Whiteley,6 Jones,' Poettmannb and the Texas Railroad Commission" are classic examples of the successful use of mathematical relationships which allow acceptable predictions of subsurface pressures, when gas is the flowing fluid. Darcy and others have derived relationships which may be used with minor modifications to predict subsurface flowing conditions in injection and water-supply wells. As previously stated, the application of the single-phase flow relationships

By J. Weijdema, D. N. Dietz

In the conventional underground combustion process (dry combustion) much heat is left behind in the swept formation and goes to rva.rte. Econonmy can be improved by heat recuperation through water injection. This is most advantageous if done at the earliest opportunity before much heat is dissiputed to cap and base rock. Water injected simultaneously with the air will flash to superheated steam, which passes through the combustion front together with the nitrogen from the air. A condensation front traveling up to three times as fast as the combustion front drives out the oil. In this type of wet combustion, the water evaporates before it reaches the combustion zone. The evaporation front travels more slowly than the combustion zone. If so much water is injected that the evaporation front overrun the combustion front, combustion in that spot will be quenched and some unburned fuel will be left behind. Air reacts with the oil farther down-stream where steam temperatures occur; at steam temperature, the air reacts rapidly with the oil. Velocity of the combustion front is increased thereby and is governed essentially by the water-injection rate. In the extreme case of high water-injection rate, a short heat wave of constant length is driven through the formation by water injection. Once this wave has been established, no more heat need be generated than that required to make up the heat losses from the short heat wave; a relatively low rate of air injection will suffice. The feasibility of partially quenched combustion has been confirmed in tube experiments. A heat wave at steam temperature is observed. Chemical analyses of flue gas indicate preferential burning of hydrogen while a carbonaceous residue is left in the formation. Introduction A disadvantage of so-called dry in situ combustion is that air-compression costs are rather high. An air consumption of about 400 std cu m/cu m (400 scf/cu ft) of formation swept is an accepted figure. This high consumption is mostly wasted since much heat is left behind in the depleted oil sand. Methods were investigated for recuperating as much as possible of the heat left behind. This paper deals only with basic principles and is confined mainly to one-dimen- sional flow without lateral heat losses; experiments were conducted in relatively narrow, well insulated tubes. If some water is injected with the air, it will turn to superheated steam in an evaporation front, which should travel behind the combustion front. The steam having passed the combustion front causes a steam drive by a condensation front that can travel faster than the combustion front. The latter needs to travel only part of the distance covered by the oil-displacing condensation front, and thus consumes less air. The water-air ratio would seem limited to that at which cold water overruns the combustion. This limitation was deliberately exceeded considerably in theory and experiments. It was found that combustion is then indeed quenched, but only locally. Farther downstream, the oxygen finds residual oil at steam temperature, which is suficiently high to ensure rapid oxidation. Thus, the combustion front uses only part of the available fuel because it is chased through the formation faster than its normal velocity. No heat is left behind. This new process is called "partially quenched combustion". At the upper limit of the water-air ratio, a small heat slug is moved through the formation by the flow of water and steam. Only a small flow of air is needed since it has only to generate sufficient heat to make up for the lateral heat losses of the short heat slug. Theory Although many factors complicate underground combustion, the processes will be presented in their simplest form. For this reason, one-dimensional flow without lateral heat losses is assumed. Heat conduction in the direction of flow also is disregarded. Under these conditions, dry combustion causes very high temperatures. The heat-carrying capacity of the gas stream is small. Heat generated by oxidation of a residual oil saturation is retained in the sand. The available fuel determines the air requirement and the temperature obtained. Accepting the often-mentioned air consumption of 400 std cu m/cu m (400 scf/cu ft) formation, we calculate a temperature of the swept sand of 1,200C (2,192F) (Fig, I). If water is injected at a modest rate with the air, it will flash to superheated steam upon contact with the heated sand. One cu m (35.31 cu ft) of hot formation will evaporate about 0.5 cu m (17.66 cu ft) of water, and thereafter will accommodate (at an estimated 0.80 saturation and an assumed 0.40 porosity) another 0.3 cu m (10.59 cu ft) of water in cold condition. As long as less than 0.5 + 0.3 = 0.8 cu m (28.25 cu ft) of water is injected for every 400 std cu m (14,125 scf) of air (water-

Jan 1, 1969

By Clarence Zener

It is customary to regard the stress-strain relation as consisting of two parts, thc elastic region and the plastic region. The essential attribute of the plastic region is the presence of a permanent set, which remains upon removal of all stresses. The essential attribute of the elastic region is the absence of such a permanent set. Absence of a permanent set does not imply a linear relation between stress and strain, nor even a single valued relation. In fact, in no real metal is stress a single valued function of strain in the elastic region. The property of a solid in virtue of which stress and strain are not uniquely related in the elastic range will be called "anelasticity." The purpose of the present article is to review and correlate the past work upon the anelasticity of metals. The following paper by W. A. West124 describes investigations upon anelastic properties of iron. Many manifestations of anelasticity have been observed, the first as early as 1835 by Weber.l,2 In his experiments Weber subjected a specimen to a constant load (or deformation) for a given time, and then suddenly removed the load. He observed that most of the deformation suddenly disappeared, but that there remained a residual deformation, which disappeared only gradually with time, as is illustrated in Fig. I. The occurrence of a residual deformation which only gradually disappeared, Weber called the elastic after-effect (Elastische Nackwir-kung). An extensive review of the early work upon elastic after-effects has been given by Auerbach.3 Another manifestation of anelasticity is the dependence of the elastic constants---e.g., Young's modulus— upon the method of measurement. Thus, if dynamic methods are used, the measured value will depend upon the frequency of oscillation. Still another manifestation is dissipation of energy attending vibration, called damping or internal friction. One objective. of metallurgical science is the understanding of the plastic and fracture properties of metals in terms of their microstructure. Through such an understanding will come the ability to design microstructure to give the desired mechanical properties. A study of anelasticity will furnish an invaluable aid in the attainment of this objective. Such studies, when properly guided, yield information regarding the relation between stress and strain in the individual components of the microstructure. In order, however, that this type of information may be obtained, it is necessary that the experimental studies of anelasticity be interpreted by the appropriate mathematical analysis. This article, therefore, starts with the mathematical formulation of anelasticity.

Jan 1, 1947

By L. W. McKeehan, W. C. Elmore

The magnetic powder method, long used for roughly mapping magnetic fields, has recently been refined1, "or investigating the microscopic variations in the surface magnetization of ferromagnetic crystals. Bitter2 first discovered regular powder patterns connected with the crystal structure of such specimens. Several other investigators:' have used Bitter's original technique, with slight modifications, to study the variation of the patterns with variations in the magnetizing field applied parallel to the surface, and their dependence upon the state of strain, of polish and of crystal cut. All of the explanations of these patterns on metallic ferromagnetics have been couched in general terms. In a preliminary report we have described an improvement ill the powder technique which led us to the discovery of a new effect throwing considerable light on the magnetic secondary structure of alpha iron4 and of nickel5 single crystals. We now report additional evidence confirming the existence and stability of a magnetic block secondary structure. Specimens The following list describes the specimens used in the present investigation. Designation Description A1 Silicon ferrite furnished to us by Dr. W. E. Ruder, of the General Electric Co., for which lie gave the following typical analysis: C, 0.05; P, 0.038; S, 0.026; Mn, 0.15; Si, 3.24. Disk, 0.60 cm. diameter, about 0.05 cm. thick. By X-ray analysis angles between disk normal and [100] 75o, [0101 76" [00l] 21o. A2 Same as A1 except: diameter 0.75 cm. A, Same as A1 except: diameter 0.68 cm.

Jan 1, 1936

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

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

Jan 1, 1967

By D. L. Albright, G. A. Colligan

An investigation has been conducted to determine the nature of the crystallographic substructure of nickel and a 1.0 wt pct Ag-Ni alloy which had been undercooled 105°C prior to solidification. A rotating back-reflection X-ray technique and modified Weissmann diffractometer were used to orient single-crystal sections from these poly-crystalline ingots and to determine the substruc-tural features of these single crystals, The sub-grain size in the pure nickel ingot is 0.5 mm diam while the silver-doped nickel subgrain size is only 0.1 mm diam. The misorientation between adjacent subgrains is approximately 1 deg of arc in both ingots, and the spread of orientation of sub-grains about the mean orientation of the crystal is 5 deg of arc in both ingots. The addition of silver results in a stable impurity substructure which is preserved during isothermal solidification and subsequent cooling to room temperature. In the absence of silver the initial impurity substructure is destroyed by dislocation interactions which produce a secondary substructure which grows to a size five times larger than the initial substructure. THE process of undercooling a metal entails cooling of the molten sample below the equilibrium freezing point without the occurrence of solidification, i.e., by exercising proper constraint over the experimental variables contributing to nucleation in the melt. The current work of walker1 and Colligan Metal reports undercooling large continuous samples of nickel by imposing appropriate restrictions upon the parameters of solidification. The silver-nickel equilibrium diagram3 reveals the presence of a monotectic reaction at 1435°C. At this temperature the maximum solid solubility of silver in nickel is approximately 3 wt pct, but this solubility decreases with decreasing temperature and the solute is rejected as a silver-rich liquid phase at temperatures below 1435°C. Thus, the 1.0 wt pct solute should be held in solution during undercooling and solidification and subsequently precipitate as a silver-rich liquid phase at grain and subgrain boundaries following solidification during cooling below 1435. This assumes no solute segregation sufficient to cause the monotectic reaction. One would expect this second phase to inhibit grain and subgrain growth by retarding dislocation motion after solidification is complete. The effectiveness of silver addition in growth retardation of high-angle grain boundaries has been demonstrated by Colligan and suprenantS4 The principal [l00] dendrite growth directions in a 2 wt pct Ag-Ni alloy undercooled 53 all radiated from the nucleation site. A similar pure nickel ingot undercooled 59°C exhibited a random orientation of [l00] dendrite directions with respect to the nucleation site. Since undoped nickel ingots do not retain any evidence of the casting or solidification texture and silver-doped ingots do retain this texture, it is reasonable to assume that considerable grain growth has taken place in the pure nickel. These particular experiments were performed in order to reveal the differences, if any, in the features of the crystallographic substructure of undoped undercooled nickel and silver-doped undercooled nickel. 1) EXPERIMENTAL PROCEDURE Data are reported on selected specimens from two massive (approximately 260 g) undercooled ingots of nickel. One ingot consisted of electrolytic nickel and the other of this same material with 1.0 wt pct addition of high-purity silver. Powder patterns were taken of both the as-received and as-solidified materials; in all cases the reflections recorded were attributable to the individual elements nickel and/or silver. Fig. 1 is a. schematic diagram of the apparatus employed for the undercooling experiments. The equipment consists in part of a fused silica crucible for containing the charge. A fused silica tube encloses the system, which is covered by a brass cap to permit partial sealing of the inert atmosphere. This cap contains a hole through which a Pt-Pt 13 pct Rh thermocouple is inserted for temperature measurement. The charge is inductively heated under a purified argon atmosphere.

Jan 1, 1963

By Charles Y. Clayton

Cast-steel runners, while not interesting from a commercial standpoint, furnish valuable material for microscopic study. Folcyl found not only the usual ingot structure, but zones of Widmannstättian structure, which he explains as due to differential crystallization. The writer, in examining nickel-steel runners, found a type of pro-eutectoid ferrite that is unusual and most probably new. The runner in question was 8.75 cm. (3.5 in.) in diameter and analyzed at its center 2.69 per cent. nickel and 0.350 per cent. carbe a and at its edge 2.62 per cent. nickel and 0.359 per cent. carbon. Th macrostruc-ture, which is the usual type, is shown in Figs. 1 and 2, which are a cross-section and the longitudinal surface, respectively. Slight segregat'ion of ferrite can be seen near the center of the segment and at other points near the edges of polyhedral grains. Stead's reagent brings out the dendritic structure within the grains as shown in Figs. 3 and 4. This texture is what would be expected of such a steel. Figs. 5 to 10 show the peculiar swirls of pro-eutectoid ferrite, the finding of which prompted this paper. These swirls, or eddies, if such a term can be applied, occur in all parts of the runner and in all parts of the individual grains. The upper left-hand figure shows this ferrite at a grain boundary; the middle left-hand figure shows the inner portion of a grain; and the lower left-hand figure shows these swirls at the edge of a grain which is also the outer edge of the runner. Straight-lined ferrite associated with swirls is found in the areas of Figs. 11 and 12. The texture of the carbon-bearing constituent of the runner is shown to some extent in Fig. 12, the pearlite being very fine or sorbitic. Higher magnification does not bring out any new features either in the peculiar ferrite or in the pearlite. Figs. 13 and 14, at 240 diameters, show the curved and straight-lined ferrite.

Jan 1, 1922

By K. Sallmann

Spurred by a variety of factors, coal flotation is making headway among the preparation plants of West Germany. The author gives some statistics on German coal flotation plants and information on the properties of the feed and quality of the derived products. Types of machines and reagents used, dewatering practices, tailings disposal, and thickening operations are covered. There is special emphasis on the many-sided problems that confront German coal preparation engineers. The coal mining industry of West Germany is concentrated in three coalfields: the first on the Ruhr and the Rhein rivers, the second on the Saar river, and the third near the frontier between Germany and the Netherlands, around the towns of Aachen and Erkelenz. The total run-of-mine production of these three coalfields amounts to 736,000 tpd which come from 145 collieries. There are 121 washeries, 43 of them with a flotation plant. The total throughput of these 43 washeries is 280,000 tpd, out of which 26,000 tons (9.3 pet of the washery feed coal) are cleaned by flotation. The capacity of the individual flotation plants varies within relatively wide limits, the average being 40 tph and the capacity of the largest flotation plant being 120 tph. During the last few years, the number and size of flotation plants have been steadily increasing, although flotation must be looked upon as an expensive and rather complex cleaning process. The considerations which have led to the widespread application of flotation may be summarized as follows: 1) In making coking coal, it is seldom possible to add uncleaned fines to the coke oven charge, as their ash content is too high. If, however, the ash content of the fines is reduced to a maximum of 7 or 8 pet, they can be admixed to the washed and crushed small sizes without difficulty. This means, naturally that revenue is increased since the price of coking fines is always higher than the price for dust or uncleaned wet fines. 2) To prevent silicosis and pneumoconiosis, water infusion and spraying of the coal are practiced much more today than ever before. As a result, moisture content of run-of-mine coal has markedly increased and the washery feed coal contains more and more slurry instead of dry dust. The price of slurry, how- ever, is very low, and in many cases it is impossible to sell filtered raw slurry with a moisture content of 20 to 25 pct and, at the same time, 20 to 25 pct of ash. Reduction of the ash content of these slurries improves the possibility of dewatering them and, in this way, also enhances the marketability of this product. 3) The new severe laws and regulations against pollution of air and rivers make it necessary to de-dust coal better than in the past and to reduce the quantity of the waste water from coal preparation plants and their solids content to a minimum. 4) Even if there were no compulsory reasons to clean the fines, flotation will often lead to an increase in the overall yield. Although not the only application, it appears that the treatment of coking fines is the primary field for the flotation process in coal preparation. It must not be overlooked, however, that a series of arguments may be advanced against flotation: 1) Flotation is an expensive process because, in addition to the cleaning operation itself, the dewatering of the froth and the disposal of the tailings is very costly. 2) Operation of a flotation plant requires well trained personnel. 3) Filtered froth has about a 20 pct moisture content and, therefore, if mixed with the cleaned small coal it causes an undesirable increase in water content of the coke oven charge. For this reason it is necessary to take additional measures for dewatering washed small coal and this, of course, entails additional expense. 4) Disposal of flotation tailings involves very difficult problems, particularly in the highly industrialized regions. An investigation covering 32 flotation plants of Western Germany shows the following composition and properties of their feed:

Jan 1, 1961

By D. W. Levinson, L. F. Mondolfo, N. A. Gjostein

MANY investigations are reported in the literature on the age hardening of Al-Mg-Zn alloys but most of them are concerned mainly with mechanical property changes. The present investigation was started to determine the structural changes in an AlMgZn alloy. The alloy composition was chosen in the existing phase diagram" so as to lie on the quasi-binary section Al-(AlZn)Mg Actually, it was found that the diagram as published was inexact at the lower temperatures and that the phase in equilibrium with aluminum at the lower temperatures is not the ternary compound. Technique The alloy used for the investigation was prepared from high purity materials and the resulting composition as determined by chemical and spectro-graphic analysis was: Zn, 6.17 pct; Mg, 2.13 pct; CU, 0.03 pct; Si, 0.009 pct; Fe, 0.005 pct; and the remainder, aluminum. An ingot -in. thick was cast, homogenized, hot and cold-rolled to strip 0.064-in. thick for dilato-metric and powder work, and to foil 0.005-in. thick for single crystal work. Solution treatment temperature for all specimens was 475°±5°C for periods of at least 1 hr, either in air furnaces or lead baths. Aging was done in oil or Pb-Bi baths controlled to within ±3°C. The aging was investigated at the following temperatures: room (30°), 130°, ZOO0, 260°, and 300°C. For the dilatometric study, the length changes were measured continuously, at temperature, using strips of alloy 10 in. long, shaped as channels to eliminate undesirable deflection due to bending. To compensate for thermal expansion and contraction due to the variations in the temperature of the aging baths, the dilatometers were built of the same alloy as the one being tested, with the same shape and size, but with material fully annealed. Gages on which 0.0005 in. could be read and 0.0001 in. estimated were used to measure the dilation. Length changes were also measured at room temperature. Strips approximately 10 in. long were solution-treated, quenched, and measured in a supermicrome-ter in which 0.0001 in. could be read and 0.00001 in. estimated. The specimens were immediately aged for a given time, remeasured, and then the cycle was repeated, including the solution treatment. The error of measurement with this technique was somewhat larger, but the results confirmed those obtained by continuous measurements. The sheet used for the dilatometric work was checked to determine grain orientation. Both X-rays and etching methods revealed a rather coarse grain size but only a negligible amount of preferred orientation. Thus, volume changes calculated from length changes are not invalidated by preferential orientation effects. Pieces of the sheet used for the dilatometric work were also used for the metal -lographic work. Filings for the powder X-ray study were produced from a homogenized piece of sheet. These filings were magnetically purged of iron, screened to 200 mesh, sealed in a Pyrex tube containing an argon atmosphere, and solution-treated. When quenching, the glass tube was broken, so that the powder dropped directly into cold water. After drying with alcohol, the powder was sealed into capillary tubes containing an argon atmosphere and then aged for the required times. In spite of all these precautions the three strongest lines of a( Al2o) appeared in all patterns, and were used as internal standards. By the use of these standards, accurate corrections for film shrinkage were obtained. For the back reflection patterns, annealed nickel powder was mixed with the specimen to act as internal standard. A preliminary investigation was made in small (57.3 mm diam) powder cameras. From these patterns the changes which took place in the solid-

Jan 1, 1957

By Donald D. Carr, Lawrence F. Rooney

Perhaps no other mineral commodity in this volume has as many uses as limestone and dolomite. These carbonate rocks are the basic building blocks of the construction industry, the material from which aggregate, cement, lime, and building stone are made. Carbonate rocks, and their derived products, are used as fluxes, glass raw material, refractories, fillers, abrasives, soil conditioners, ingredients in a host of chemical processes, and much more. Although the use of limestone and dolomite goes back before recorded history, new uses and products are continually being found. Carbonate rocks form about 15% of the earth's sedimentary crust and are widely available for exploitation. Found extensively on all continents, they are quarried and mined from formations that range in age from Precambrian to Recent. Reserves of carbonate rock are large and will last indefinitely, although high-purity deposits may be absent or have limited availability in certain areas. Limestone and dolomite are so useful and so abundant that in 1981 about 644 million tons were produced in the United States. In fact, about 75% of all stone quarried or mined in the United States was carbonate rock. Sand and gravel was the only mineral commodity produced in greater quantity. In this chapter we have sought to provide the general reader an overview of carbonate rocks, their composition, distribution, production, and uses, with emphasis on developments since 1960. In doing so we borrowed extensively from our report on the applied geology of limestone and dolomite (Rooney and Carr, 1971). The literature on the limestone and dolomite resources of the United States and Canada is so vast and diverse that one can easily become mired down in print. We tried to list those references that are easily accessible and that provide the economic geologist with a starting point for more intensive study. The table listing selected references on limestone and dolomite resources in Canada and the United States reflects our attempt to be selective rather than exhaustive and to direct the reader to the best sources of detailed information. Geology Mineralogy The principal carbonate rocks used by industry are limestone and dolomite. Limestones are sedimentary rocks composed mostly of the mineral calcite (CaCO3) and dolomites are sedimentary rocks composed mostly of the mineral dolomite (CaCO3 • MgCO3). Aragonite (CaCO3), which has the same chemical composition as calcite but a different crystal structure, is economically important only in modern deposits, such as oyster shells and oolites. Aragonite is metastable and alters to calcite in time. Some other carbonate minerals, notably siderite (FeCO3), ankerite (Ca2MgFe (CO3)4), and magnesite (MgCO3), are commonly found associated with limestones and dolomites but generally in minor amounts. Because of their similar physical properties, the carbonate minerals are not easily distinguished one from the other. Specific gravity,

Jan 1, 1983

By C. M. Schwartz, A. E. Austin, W. B. Wilson

High-temperature X-ray diffraction studies were conducted with Th-U alloys with up to 10 wt pet U. The solid solubility of uranium in thorium as a function of temperature was determined by the method of lattice parameters. Thorium will dissolve up to 2.5 wt pet U at 950°, 4.5 wt pet U at 1150°, and 7.5 wt pet U at 1250°C. Determinations were made of the temperature of the transition of thorium and of the effect of uranium upon the transition. The a to ß transition for thorium was observed to occur at 1330' ±20°C. Mean coefficients of expansion were calculated for thorium and two alloys, and for ThO2 in contact with the thorium, using X-ray lattice-parameter data. Values obtained at 950° C for thorium and Tho2 were 12.1 and 9.40 X 10-6 per OC, respectively. Impurities obtained during the X-ray exposure were identified by diffraction and were essentially Tho2 and ThC, with two additional unknown phases being detected. The effect of the impurities upon the results is discussed. DIRECT investigation (i.e., high-temperature X-ray diffraction studies) of the phase diagram of thorium-rich uranium alloys has been shown to be necessary since recent work1 - has disclosed the presence of an allotropic transformation near 1400°C in pure thorium with the room temperature face-centered-cubic phase transforming to a body-cen-tered-cubic structure at the elevated temperature. The effect upon the transition of the addition of uranium to thorium and of the solubility of uranium in thorium at high temperatures remained unknown, yet was of interest in understanding fabrication procedures and elevated temperature use. The present work was undertaken to provide information in this area by determining the transition temperature, the effect of uranium on the transition temperature, and the solubility of uranium in thorium as a function of temperature. Experimental Work The high-temperature diffraction data were obtained using a camera especially designed for the purpose3 and capable of reaching temperatures in excess of 2000°C at pressures as low as 1 x 10." mm Hg. Temperature regulation was provided by regulating the power input to ±0.1 pet variation, and by regulating the water flow through the camera jacket to provide a constant thermal load. The X-ray sample was a rod nominally 80 mil diam, which was further turned down to 20 mil and then etched to 18 mil over 1/2 in. of one end. This was placed in the sample holder and mounted on the camera so that the smaller part was surrounded by a cylindrical tantalum-sheet radiation-type heating element. Diffraction from the sample was recorded on film after passing through a slot in the heating element and radiation-baffle shield and through beryllium vacuum windows. The X-ray film mounting was of the Straumanis type4 with a camera diameter of 114.59 mm. Since previous work of Chiotti' indicated that impurities considerably alter the transition temperature, chemical analysis of the arc melted iodide crystal-bar thorium samples was obtained prior to testing. The analysis disclosed the material to contain as low as 0.001 ±0,0002 wt pet H and 0.007 ±0.001 wt pet 0. Carbon was 0.003 wt pet and nitrogen less than 0.002 wt pet. This material was sealed in mild steel in an inert atmosphere and subsequently hot rolled to 3/8-in. diam rods at a temperature of 732°C. Following removal of the jacket, the material was pickled and cold swaged to 1/8-in. rods, from which the diffraction samples were prepared. The alloys were similarly prepared, with the uranium being added during arc melting. The uranium analyses of the alloys prepared appear in Table I. The experimental procedure for diffraction examination of the three samples of high-purity thorium differed from those of the Th-U alloys. The original practice, later modified, consisted of pumping down the camera with the diffusion pump on and then admitting liquid nitrogen to the cold trap of the system. This was modified for the Th-U alloys by maintaining liquid nitrogen in the cold trap at all times before and while the diffusion pump was heated. This minor change produced a reduction in the amount of carbon pickup by the sample during exposure to the diffusion-pump vapors. The sample was brought to the desired test temperature and exposed for 21/2 hr at pressures which were usually 2 x 10-6 mm Hg, or lower. Exposures were made at

Jan 1, 1959

By Fred C. Bond

MOST investigators are aware of the present unsatisfactory investigatorsstate of information concerning the fundamentals of crushing and grinding. Considerable scattered empirical data exist, which andare useful for predicting machine performance and give acceptable accuracy when the installations and materials compared are quite similar. However, there is no widely accepted unifying principle or theory that can explain satisfactorily the actual energy input necessary canexplain commercial installations, or can greatly extend the range of empirical comparisons. Two mutually contradictory theories have long existed in the literature, the Rittinger and Kick. They were derived from different viewpoints and logically lead to different results. The Rittinger theory is the older and more widely accepted.'TheRittinger In its first form, as stated by P. R. Ritted.'tinger, it postulates that the useful work done in crushing and grinding is directly proportional to the new surface area produced and hence inversely proportional to the product diameter. In its second form it has been amplified and enlarged to include the concept of surface energy; in this form it was precisely stated by A. M. Gaudin' as follows: "The efficiency of a comminution operation is the ratio of the surface energy produced to the kinetic energy expended." According to the theory in its second form, measurements of the surface areas of the feed and product and determinations of the surface energy per unit of new surface area produced give the useful work accomplished. Computations using the best values of surface energy obtainable indicate that perhaps 99 pct of the work input in crushing and grinding is wasted. However, no method of comminution has yet been devised which results in a reasonably high mechanical efficiency under this definition. Laboratory tests have been reported- hat support the theory in its first form by indicating that the new surface produced in different grinds is proportional to the work input. However, most of these tests employ an unnatural feed consisting either of screened particles of one sieve size or a scalped feed which has had the fines removed. In these cases the proportion of work done on the finer product particles is greatly increased and distorted beyond that to be expected with a normal feed containing the natural fines. Tests on pure crystallized quartz are likely to be misleading, since it does not follow the regular breakage pattern of most materials but is regularrelativelybreakage harder to grind patternat the finer sizes, as will be shown later. This theory appears to be indefensible mathematically, since work is the product of force multiplied by distance, and the distance factor (particle deformation before breakage) is ignored. The Kick theory4 is based primarily upon the stress-strain diagram of cubes under compression, or the deformation factor. It states that the work required is proportional to the reduction in volume of the particles concerned. Where F represents the diameter of the feed particles and P is the diameter of the product particles, the reduction ratio Rr is F/P, and according to Kick the work input required for reduction to different sizes is proportional to log Rr /log 2." The Kick theory is mathematically more tenable than the Rittinger when cubes under compression are considered, but it obviously fails to assign a sufficient proportion of the total work in reduction to the production of fine particles. According to the Rittinger theory as demonstrated by the theoretical breakage of cubes the new surface produced, and consequently the useful work input, is proportional to Rr-l.V f a given reduction takes place in two or more stages, the overall reduction ratio is the product of the Rr values for each stage, and the sum of the work accomplished in all stages is proportional to the sum of each Rr-1 value multiplied by the relative surface area before each reduction stage. It appears that neither the Rittinger theory, which is concerned only with surface, nor the Kick theory, which is concerned only with volume, can be completely correct. Crushing and grinding are concerned both with surface and volume; the absorption of evenly applied stresses is proportional to the volume concerned, but breakage starts with a crack tip, usually on the surface, and the concentration of stresses on the surface motivates the formation of the crack tips. The evaluation of grinding results in terms of surface tons per kw-hr, based upon screen analysis, involves an assumption of the surface area of the subsieve product, which may cause important errors. The evaluation in terms of kw-hr per net ton of —200 mesh produced often leads to erroneous results when grinds of appreciably different fineness are compared, since the amount of —200 mesh material produced varies with the size distribution characteristics of the feed. This paper is concerned primarily with the development, proof, and application of a new Third Theory, which should eliminate the objections to the two old theories and serve as a practical unifying principle for comminution in all size ranges. Both of the old theories have been remarkably barren of practical results when applied to actual crushing and grinding installations. The need for a new satisfactory theory is more acute than those not directly concerned with crushing and grinding calculations can realize. In developing a new theory it is first necessary to re-examine critically the assumptions underlying

Jan 1, 1953

By G. S. Tint, M. Herman, V. V. Damiano

Dislocation arrays and substructures were studied in cadmium doped zinc crystals using a newly devised etching technique. Cadmium precipitates delineating the dislocations were revealed by etching a surface closely parallel to the (0001) slip plane. Cinephotomicrography of the continuous etching process revealed the three-dimensional aspects of dislocations in the bulk crystal. Dislocation etch patterns were studied in both deformed and annealed crystals after suitable aging at room temperature. The effect of annealing was evidenced by a rearrangement of the dislocations into low-angle boundaries and hexagonal networks. ETCH pit techniques have been used extensively to study dislocations in both deformed and annealed bulk metal crystals. Ideally one hopes to obtain a one-to-one correspondence between the etch pits and the points of emergence of the dislocations at the surface. One then attempts to deduce the way in which dislocations are arranged in the bulk crystal from the arrangement of etch pits on the surface. It is clear that one can obtain only limited information of the dislocation configurations inside the crystal from etch pit studies of single surfaces. Considerably more information is obtained if one is able to follow the course of the dislocations through the crystal using progressive etching technique. Techniques of this sort were used by Gilmanl to study dislocations on the slip planes of NaCl crystals and by Damiano and Tint2 to study dislocation arrangement in zinc crystals grown from the melt. The present paper makes use of a technique first described by Tint and Damiano3 to observe and continuously record the dislocation structures which appear while a crystal surface was being progressively etched. Studies were made on cleaved (0001) surfaces to reveal the dislocations along their length on the surface closely parallel to the slip plane. The technique for revealing segments of dislocations along their length by etching is well known. Wilsdorf and Kuhlmann-wilsdorf4 revealed disloca- tions along their length in aluminum containing a few percent copper, when precipitates segregated along the dislocations. The technique was used by Low and Guard5 to study dislocation configurations on the slip plane in Fe-Si alloys containing carbon. In the present work the technique was applied to zinc containing cadmium since it was shown by Gil-man6 that a cadmium-rich phase could be made to precipitate from supersaturated solutions along dislocations in zinc. Segments of dislocations delineated by the precipitates were revealed by etching a surface prepared by cleaving the crystal. The three-dimensional nature of dislocations and substructures was thus studied from the cinephotomicro-graphic record of the continuous etching process. EXPERIMENTAL Single crystals of zinc containing the order of 0.1 pct Cd were prepared by slowly lowering a graphite crucible containing the melt through a temperature gradient of 15°C per cm at a rate of 1.5 X 10-3 cm per sec. "As grown" crystals were aged for periods of 1 month at room temperature, then cleaved in liquid nitrogen, and etched according to the procedure used by Gilman.' The etchant containing 32 g of CrO3, 6 g of hydrated Na2SO3 in 100 ml of water behaved as a chemical polish for zinc and etch pits were produced at the site of precipitates or inclusions. After the precipitates or inclusions were removed from the surface, the etch pits left behind were eventually polished smooth. This behavior enabled one to continuously observe the surface while the specimen was immersed in the etchant. Best results were obtained when the specimen surface was vertical and the reaction products of polishing were continuously removed by gravitational convection. Some crystals were heavily deformed in excess of 25 pct strain, others were lightly deformed the order of a few pct by compression such that the deformation occurred essentially by basal glide. Some crystals were etched immediately after deformation, others were allowed to age at room temperature for several weeks prior to etching. Heavily deformed crystals were annealed at various temperatures and etched on the cleavage plane immediately after annealing, others were allowed to age at room temperature for several weeks prior to etching. The etched structures of deformed and annealed structures were studied. Similar experiments were conducted on 99.9999 pct pure zone refined Tadanac zinc crystals which

Jan 1, 1963

By R. C. Padfield

Experience over a 3-year period in Bethlehem Steel Corporation's plants has demonstrated the reliability of open-hearth roofs of bonded sprung-arch constructzon with burned basic brick. The design principles lor constructing these roofs include a minimum hot-strength requirement for the basic brick, expansion allowances that extend the full roof thickness, structural members to control arch contour, and a specified minimum roof rise. The greater stability of bonded roofs is explained in terms of the basic stress patterns of ring constrution and bonded construction. PRIOR to the development of successful sprung-arch roofs of basic brick, the majority of open-hearth furnaces in the United States were operated with sprung-arch roofs built of silica brick. Although many silica roofs used on open-hearth furnaces were ring-arch construction, Bethlehem Steel Corp. used bonded-arch construction because of its greater stability. In ring construction, each ring of brick is separately keyed and comprises an independent arch with the straight joints between rings traverse to the longitudinal axis of the furnace. In bonded construction, the bricks are laid in rows starting from the skewbacks so that the straight joints run parallel to the longitudinal axis of the furnace. Each brick in a given row is laid so that it spans the joint between two bricks in the row beneath it. Thus, the transverse joints across the arch are broken and the arch rings are thereby interlocked or bonded. When basic roofs were first being developed, the basic brick that were available had low hot strength. Such brick could not be safely used in sprung-arch construction without some means of suspending them. With the development of higher firing techniques by brick manufacturers and the recently introduced direct bonded bricks with high hot strength, the use of burned basic brick in sprung-arch roofs became feasible. The availability of high hot strength basic brick coupled with the potentially lower cost and proven stability of bonded construction prompted Bethlehem's Research Department to study the possibility of using basic brick in bonded roofs. With the full cooperation of plant ceramic engineers and open-hearth superintendents, particularly in 3 years of fur-nace trials, we developed the design criteria for bonded roofs and the corresponding property requirements for the basic brick that are discussed in this paper. DESIGN PRINCIPLES OF SPRUNG-ARCH BRICK ROOFS Stresses in Fixed Arches. A sprung-arch open-hearth furnace roof is generally built on rigidly held skewbacks. The constraint of the fixed support at each end adds a bending moment to the horizontal and vertical reactions at the ends of the arch. Fig. 11 shows the positive direction of forces acting on an arch fixed at both ends. Fixed arches can be analyzed when the members are continuous and have elastic properties. However, brick are inelastic, and arches built with individual brick segments cannot carry tensile stresses. Therefore, for practical solution of brick arches, empirical formulas have been derived from elastic theory that place design restrictions on arch dimensions to avoid development of tensile stresses. McDowell2 cites three main conditions for stability in sprung brick arches: 1) the thrust line of the arch should be maintained in the middle third of the thickness to avoid tensile stresses and resulting open joints in inner and outer curves of the arch; 2) the angle between the line of thrust at any joint and a line perpendicular to the joint must not exceed the angle of repose between brick; and 3) the maximum pressure at any point must not exceed the strength of the arch materials at furnace operating temperatures. The first and third conditions are particularly important in designing sprung-arch basic roofs because of the comparatively low hot strength of basic brick. According to McDowell's equation, if the thrust line is maintained within the middle third of the arch thickness, the unit pressure is obtained as follows: where p = unit pressure in psi, F, = resultant thrust normal to skewback in pounds per foot, t = arch thickness in inches, and z = distance in inches of thrust line from arch axis. When the resultant thrust normal to the skewback acts along the arch axis, z equals zero and unit pressure is simply the thrust divided by the cross-sectional area. If the thrust line moves to the limits of the middle third of the arch thickness, beyond which tensile forces would develop, z then equals one-sixth of the arch thickness and the unit pressure is double that when the thrust line is acting

Jan 1, 1968

By J. G. Richardson, J. W. Graham

The purpose of this paper is to present the results of theoretical and experimental studies of water imbibition. The imbibition processes are involved in recovery of oil from stratified and fractured-matrix formations in natural water drives and water flooding. An understanding of the role of inhibition in implementing the recovery of oil from such formations is deemed essential to proper control of these reservoirs to achieve maximum recovery. The theoretical studies involved development of the differential equations which describe the spontaneous imbibition of water by an oil-saturated rock. The dependence of the rate of water intake by the rock on the permeability, interfacial tension, contact angles, fluid viscosities and fluid saturatiorls is discussed. A few experiments were performed using core samples to determine the effects of core length and presence of a free gas suturation. The role of water imbibition in recovery of oil from a fractured-matrix reservoir by water flooding was investigated by use of a laboratory model. This model was scaled to represent one element of a frac-tured-matrix formation. Water floods were made at various rates with several fracture widths. Interpretations were made of the behavior expected in a system containing many matrix blocks. The presence of a free gas sntu.ration was found to reduce the rate of water imbibition. In the reservoir prototype of the fractured-matrix model, water imbibition rather than direct displacement by water was the dominant mechanism in the recovery of oil at low rates. INTRODUCTION Imbibition may be defined as the spontaneous taking up of a liquid by a porous solid. The spontaneous process of imbibition occurs when the fuid-filled solid is immersed or brought in contact with another fluid which preferentially wets the solid. In the process of wetting and flowing into the solid, the imbibing fluid displaces the non-wetting resident fluid. Common examples of this phenomenon are dry bricks soaking up water and expelling air, a blotter soaking up ink and expelling air and reservoir rock soaking up water and expelling oil. As increasingly better lithological descriptions have been made of the characteristics of petroleum-bearing formations, it has become obvious that imbibition phenomena which were once considered laboratory curiosities are of practical importance. For instance, in reservoirs composed of water-wet sand strata of different permeability in intimate contact, the tendency of water to channel through the more permeable stratum is offset by the tendency for water to imbibe into the tight sand and expel oil into the coarse sand. Also, in fractured-matrix formations the tendency of water to channel through the fractures is offset by water-wet matrix blocks. As some imbibition of the water into the of the largest fields in the world are fractured-matrix reservoirs, it has become increasingly important to understand all the factors involved in the imbibition process. Examples of fractured-matrix reservoirs are the Spraberry field in West Texas which produces from a fractured sandstone', the giant Kirkuk field in Iran', the Dukhan field in Qatar, Persian Gulf2, and the Masjid-I-Sula-main and the Haft-Kel fields in Southwestern Iran, which produce from fissured limestone3. Research into recovery of oil from fractured-matrix formations was stimulated by the rapid decline of oil productivity of wells in the Spraberry formation. One result of this research was the water imbibition process developed by the Atlantic Refining Co.4 Another idea was that much of the Spraberry oil could be recovered by conventional water-flooding procedures5. Subsequently, pilot floods were conducted in this field to test the feasibility of these ideas. It was felt that an understanding of the role played by imbibition processes in displacement of oil from a fractured-matrix reservoir could not be obtained from field data alone because of the many complicating factors and uncertainties involved. Therefore, theoretical and laboratory studies were undertaken to provide this understanding. Study of the equations which describe the linear, countercurrent imbibition process provided an insight into the role of various factors in the process, such as the permeability of rock and inter-facial tension. In addition to the theoretical studies, imbibition experiments were conducted with core samples to determine the effect on the rate of imbibition of such variables as core length and free gas saturation. The principal experimental studies were conducted by water flooding a scaled model of an clement of a frac-tu red-matrix reservoir to evaluate

By R. K. Hopkins

Fox a great many years fusion welding has been used in and around petroleum refineries, but it is only within six or seven years that the more important pressure vessels have been constructed by this process, because before that time the properties of fusion welds would not withstand such rigorous service. Since the adoption of fusion welding for the construction of this equipment, the refiner has required pressure vessels suitable for operation over a very wide range of conditions. On the one hand, vessels must operate at extremely high temperatures, in the range of 950° to 1000° F., and on the other vessels must be suitable for operation at sub-zero temperatures down as low as -75° F. Also, vessels are required suitable for operation at pressures upwards of 1000 lb. per sq. in., and as low as a 29-in. vacuum. In addition, vessels are required to withstand the attack of very corrosive mediums. It has been a rather difficult task for the fabricator to meet all of these requirements, but as a result of the extensive research carried on by steel manufacturers and several fabricators of class I vessels, practically all of these demands have been met. In order to meet the refiners' requirements for this wide range of conditions, the fabricator has worked closely with the metallurgist. This has enabled him to choose the proper base metal for each service condition, but it has been the fabricator's problem to develop a welding rod and welding technique, as well as a heat-treatment, that would produce in the welded vessel characteristics in and around the weld comparable to those in the base metal. Where corrosion is not a serious problem, and where the operating temperatures are not too high, ordinary carbon steel has served very well. But when corrosion is serious, and/or when the temperatures are either very high or very low, it is necessary to use some form of alloy steel to give satisfactory service.

Jan 1, 1935

By L. R. Shoenberger

Boron has been used to produce nonaging low-carbon sheet steel. Retention of the necessary minimum amount of about 0.006 pet partially killed the steel. Amounts exceeding about 0.012 pet increased the degree of deoxidotion, piping tendencies, and possibility of hot tearing in primary rolling. Semikilled practice resulted in good ingot yields and satisfactory surface quality. Aluminum added with the boron provided a protective de-oxidizer. Good drawobility was indicated by performances of the steel in a limited number of deep-drawing trials. Some problems with hot-tearing and boron-analysis procedures were overcome. Metal lographically, the boron semikilled steels revealed some structures not usually found in plain low-carbon steels. IN 1943 Low and Gensamer1 reported that strain aging, which hardens and embrittles ordinary low-carbon rimmed steel, was due to nitrogen and carbon, and that oxygen played a relatively unimportant role. Since then, many investigators have substantiated their findings and indicated that nitrogen is particularly potent. Commercially, today's most widely produced non-aging sheet steels for deep drawing are either aluminum killed or vanadium rimmed types. The difference in deoxidation practice, alone, is evidence that oxygen is apparently not an important consideration in control of strain aging. The fact that nitrogen is important is apparent in the consideration that has been given, knowingly or unknowingly, to the amount combined with aluminum and vanadium. Patents were granted to Hayes and Griffis2 for the processing of aluminum-killed steel, and to Epstein" for the manufacture of vanadium rimmed material. Certain prescribed steps in producing these steels can be correlated with the formation of the respective nitrides within certain temperature ranges below the usual hot-finishing temperatures. The potential nonaging properties of either type can be reduced or suppressed by cooling too rapidly to permit the aluminum or vanadium to combine with nitrogen. Subsequent suberitical annealing of the cold-rolled strip, however, normally forms the nitrides and produces the resistance to strain aging. Titanium-killed nonaging steel, described by Comstock,1 forms a nitride in the molten state and is essentially nonaging throughout its processing. Zirconium-killed steel, which was investigated briefly by the author,* appeared to have similar nitride- forming characteristics. It is known" that chromium can produce nonaging rimmed steel, but relatively little is known of the potentialities of some of the other nitride-forming elements such as boron, silicon, columbium, and cerium. In attempting to develop a new nonaging cold-rolled sheet steel with good drawability, the following factors were considered pertinent. Such a steel would necessarily have a low carbon content and therefore have a relatively high degree of oxidation when made in a basic open-hearth furnace. If the denitriding element were also a deoxidizer, a part of the addition would be lost as oxide. The degree of deoxidation would determine whether the steel is rimmed, semikilled or killed, and also could be expected to have an important bearing on ingot yields and ultimate surface quality. Assuming that the pattern for the production of cold-rolled sheets would not be changed to any great extent, the nitride must form in the molten steel, in hot rolling, in subsequent cooling, or in annealing. The nitride, once formed, should resist dissociation and be stable in the final product. Usually an excess of the nitride-forming element is required to combine with sufficient nitrogen. If the element used is a strong ferrite strengthener, a small excess may markedly decrease drawability. With aluminum and vanadium, about 0.03 to 0.05 pct in the steel is preferred. Epstein has said" that about 0.30 pct chromium is required. Titanium nonaging steels are hard unless a sufficient amount (about 0.30 pct) is added also to combine with the carbon. The cost of the necessary amounts of these latter two elements discourages commercial acceptance. Silicon was considered as a possible nitride former, but since amounts up to 0.10 pct in rimmed and semikilled steels do not induce marked resistance to strain aging, larger amounts are apparently required, which would tend to harden and strengthen the ferrite. Of the other elements mentioned, all but boron are expensive heavy-metal elements. Stoichi-ometrically, almost an equal weight of boron would be required to combine with the nitrogen—-ordinarily about 0.003 to 0.006 pct in scrap-practice open-hearth steels. Boron is a slightly stronger deoxidizer than carbon but is less powerful than zirconium, aluminum, or titanium. Thus a rimmed-steel practice might be possible. There is much in the technical literature concerning the hardenability effects of minute amounts of boron in killed steels but very little about its behavior in low-carbon material—particularly as a ferrite strengthener. The available data indicated a need for better information concerning the effects of boron in low-carbon strip steels. Experimental Work Development of a Boron-Treated Nonaging Strip Steel—Initial attempts to produce a boron-rimmed strip steel employed 3-ton basic open-hearth heats which could be teemed into molds large enough to sustain a normal rimming action. Boron as ferro-boron was added to the ladle in small amounts because of the reported hot-short character of aluminum-killed heat-treating grades containing more than about 0.005 pct boron. Actually, the amounts used, i.e., 1/8 and 1/4 lb per ton, would be large for

Jan 1, 1959