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By J. L. Huitt, B. B. McGlothlin, D. K. Lowe

Published correlations for the principal aspects of hydraulic fracturing were combined into a digital computer program to facilitate the study of interrelated variables. The computer program includes individual relationships for fracture width during pumping, fracture area generated, propping agent embedment, flow capacities of propped fractures and transport of propping agents in horizontal fractures. The effects of more than 20 treatment and formation parameters on the predicted results of hydraulic fracturing treatments were studied. The effects of these parameters were determined for (I) fracture width during injection, (2) fracture width after the overburden comes to rest on the propping agents, assumed not to be crushed, (3) generated and propped fracture area, (4) location and concentration of propping agents in the fracture when injection ceases, (5) flow capacities of the various propped sections of the fracture and (6) expected increase in the well productivity. The effects of propping agent, formation and fracturing fluid parameters on well productivity are discussed. The parameters that were found to have the most pronounced effects on hydraulic fracturing treat~nents are injection rate, treatment volume, fracturing fluid coefficient, size and amount of propping agent, spearhead volume, well drainage radius and formation capacity. INTRODUCTION Many correlations have been published for predicting effects of various parameters that are considered in the design of hydraulic fracturing treatments. The Carter equation' can be used to predict generated fracture radius as a function of fracture width, fracturing fluid leakoff and other parameters. Fracture width can be determined by use of the Perkins and Kern correlation' in which the fracture width is related to the fracture radius, fluid injection rate and certain formation and fracturing fluid parameters. Wahl and Lowe et aL4 have reported methods of predicting the location of propping agents in fractures when pumping ceases. The former study is applicable to the case where the ratio of propping agent diameter to fracture width is less than 0.1. The latter is applicable when this ratio is greater than 0.1. These studies showed that the propping agent placement in horizontal-radial fractures depends principally on how the individual particles are transported in the fracture by the carrying fluid. Particle transport in fractures is determined by local fluid velocity in the fracture, fluid and particle properties, and the size of the particle relative to the fracture width. The distribution of propping agents, effective overburden pressure and formation rock strength control the propped fracture width6 by controlling the extent to which the propping agent particles embed into the fracture faces. From the distribution of propping agents and the propped fracture width, fracture flow capacities can be calculated or the various regions of the fracture. The flow capacities and the radial extent of these regions can be combined with reservoir information to predict the productivity increases for fractured wells. In all these studies, the effects of certain treatment and/ or reservoir parameters on one facet of fracturing can be predicted only if other facets which the parameters affect are fixed. For instance, fracture width and radius are interrelated; that is, to calculate the value of one, the value of the other must be known. Also, some parameters influence more than one aspect of fracturing. For example, prop-pant transport is a function of both fracture width and fluid viscosity. but fracture width is itself a function of fluid viscosity. Since these calculations are complex and the parameters interrelated, it is not possible to write an equation with which the over-all effects of treatment parameters can be solved explicitly. For these reasons, the correlations for determining the effects of the parameters which are most significant in hydraulic fracturing treatments have been incorporated into a digital computer program. COMPUTER PROGRAM The program, which was written for an IBM 7094 computer, can be used to predict results of most of the combinations and values for the treatment parameters that are ordinarily considered for fracturing treatments. A spearhead of fracturing fluid and a propping agent-carrying fluid with different fluid properties can be taken into account. Also, the total volumes and relative amounts of the spearhead and carrying fluids can be varied. Two different propping agents (as used in tail-in operations) and a wide range of formation properties and injection rates are considered. The computer program (Fig. 12) consists of several sets of calculations. First, the final flooded fracture radius and average fracture width at the cessation of pumping are calculated. This is done by simultaneous solution of the Perkins and Kern fracture width equation and the Carter equation for flooded fracture radius (equations used in the computer program appear in the Appendix). The next step is to determine local fluid velocity in the fracture as a function of time and radius. Since it is not possible to write this function in closed form expression, a table of velocity values is generated by the program and stored for subsequent use. The time span from the beginning of

By L. B. Gittinger

Sulfur is a nonmetallic element widely distributed in nature. It constitutes 0.06% of the earth's crust but only a very small portion occurs in sufficiently concentrated amounts to justify mining. Sulfur occurs in practically all animal and plant life. It constitutes approximately 0.09% of the elements in the oceans; it has been found in meteorites. Sulfur was known and used by man before recorded history. The American Chemical Society approved spelling for the element is sulfur. The English spelling sulphur is used commercially in the United States. In ancient times, sulfur was called brimstone, literally "burning stone." Today the term brimstone is used interchangeably with the term elemental sulfur. Sulfur is found naturally in the elemental form in subsurface deposits associated with gypsum and anhydrite in salt domes and sedimentary formations in evaporite basins and in solfatara-type deposits associated with volcanoes and mineral springs. Sulfur occurs also in molecular combination in ferrous sulfides (pyrites and pyrrhotite) and nonferrous sulfides (copper, lead, zinc, and nickel), and in mineral sulfates (gypsum and anhydrite); as hydrogen sulfide contaminant in natural gas; as organic compounds in crude oil and tar sands; and as pyrite and organic compounds in coal and oil shales. Sulfur resources are abundant and exist throughout the world but the extent to which they can be classified as reserves is greatly circumscribed by prevailing prices and technology. Estimates of world sulfur reserves are compiled by the U.S. Bureau of Mines. A compilation of reserves by area and source of sulfur published in 1970 and presented here as [Table 1] totaled 2.47 billion tons (Lewis, 1970). The effect of the decline in prices which has occurred since the earlier estimate is dramatically illustrated by the 1972 estimate of the U.S. Dept. of the Interior which shows world sulfur reserves of only 1.2 billion tons (Anon., 1972d). Sulfur is produced commercially from one or more sources in nearly 70 countries of the world. World production of sulfur in all forms totaled 41.6 million tons in 1971. (Sulfur statistics given in this chapter are long tons.) Native deposits, sulfides and oil and gas contributed, respectively, 31, 41, and 25% of world production (Table 2). Of the sulfur produced from native deposits, salt domes accounted for 54% and evaporite basin deposits, 44%. Volcanic deposits are of little significance except for local consumption. The past two decades have seen important shifts in the world's sulfur sources. In 1950, native deposits and sulfides each supplied about one-half of the world's production. During the 1950s, sulfur recovered from oil and natural gas grew rapidly, representing about 10% of the total by 1960. Since then, the petroleum industry has continued to increase its relative importance as a source of sulfur, representing more than 30% at 1972 year-end. Sulfur is generally classified as elemental or nonelemental for statistical purposes. Elemental sulfur is sulfur produced in the pure, uncombined form. It includes production from native deposits, as well as that recovered in the elemental form from oil and natural gas or other sulfur-bearing materials. When produced from other than native deposits, it is generally referred to as recovered elemental sulfur. Nonelemental sulfur is that which is utilized commercially in molecular combination with other elements, such as sulfides or sulfates. Elemental sulfur is being produced from salt dome deposits in the Gulf Coast region of the United States and the Isthmus of Tehuantepec in Mexico, and from evaporite basin deposits in west Texas, Poland, Sicily,

Jan 1, 1975

By Albert E. Reed

The development of the modern highspeed vibrating screen, together with the increasing availability of long-lasting stainless-steel screen cloth for relatively fine-mesh separations, means that more screen circuits will be used in the future. It seems pertinent therefore to examine a few characteristics of screen-circuit products, and especially the points of difference as compared with products of classifier circuits. The most noticeable change that takes place when substituting screening for classification in a grinding circuit is a substantial drop in the circulating load, owing to the greater ease with which the "fines" leave the circuit. Where circulating loads of 500 to 600 per cent are considered fairly normal in classifier grinding circuits, the grinding circuit equipped with screens for equivalent work will have a circulating load of only 20 to 75 per cent. As a result, the products of screen circuits will show a minimum of overgrinding or sliming as compared with a classifier circuit. The desirability of this characteristic will naturally vary according to the metallurgical requirement in each case. Because screen separations make a sharper division according to particle size, the products of screen circuits can be expected to show greater crowding of particles near the point of separation. These changes in product characteristics are so important that other factors, both in the grinding and concentration processes must be adjusted if the operator is to take full advantage of the increased tonnages and higher efficiencies available to him through the use of the screen circuit. One factor that too often is overlooked when changing to screen circuits is the importance of adjusting the ball-mill or rod-mill charge, to compensate for: (I) increased tonnage of new feed, (2) decreased circulating load, or (3) more granular character of feed. These same factors should also be taken into consideration for their effect on the various types of concentration or flotation equipment that may follow the screen circuit. Over a period of years, this equipment has generally been designed and adjusted to the product of the classifier, therefore it seems obvious that some research on the adjustment and adaptation of concentrating and flotation equipment to screen-circuit products will be most profitable to the operators. To illustrate the points mentioned above, the results from three recent installations follow, with data on the comparative characteristics of screen and classifier circuits. A range of separation from 10 to 48 mesh has been chosen, using two general types of screening equipment and two types of classifiers. The first of the installations of which the results are to be examined is that of an iron-ore installation where eastern magnetite was being concentrated prior to sintering. Fig. I shows the original grinding circuit, using classification, while Fig. 2 shows the same circuit equipped with a

Jan 1, 1947

By Terkel Rosenqvist

THE desulphurization of molten iron and steel is a very complicated process. One way to arrive at a better understanding of this process is to break it down into several simpler chemical processes that can be studied individually in the laboratory. For a study of the different factors that influence the equilibrium distribution of sulphur between liquid metals and slags, several simpler equilibria may be investigated. One very important subject is the determination of the escaping tendency of sulphur in the liquid metal and its dependency on temperature and composition of the melt. Several papers in this field have recently been published.', ' Another subject is the study of the sulphur capacity of the slag. A molten slag is indeed complex, and even if sulphur distribution data for a large variety of molten slags may give empirical data about their desulphurizing power, the importance of the individual components is still not quite clear. It is accepted generally that lime is the most important desulphurizing component in the slag. The present investigation has as its purpose to study the desulphurizing power of lime in its standard state, and to provide a basis for thermodynamic calculations of the desulphurizing power of various lime-containing slags. The standard state of lime at steelmaking temperatures is solid calcium oxide, CaO. It can react with sulphur to form solid calcium sulphide, CaS. The relative stability of calcium oxide and calcium sulphide is expressed by the free energy of the reaction: 2Ca0 (s) + S1 (g) = 2CaS (s) + O2 (g) The existing free energy data for this reaction, listed by Kelley5 nd Osborn,' are uncertain to about 10 kcal and are of limited value for a calculation of equilibrium constants. Under the conditions prevailing in a melting furnace, the sulphur pressure may be expressed conveniently by the ratio H,S/H2 and the oxygen pressure by the ratio H,O/H, (or CO,/CO). The desulphurizing power of calcium oxide may, therefore, be studied by the reaction CaO + HIS = CaS + H2O. A study of this reaction may be complicated by certain side reactions: Water vapor and hydrogen sulphide may react. to form sulphur dioxide, and calcium sulphide may be oxidized to calcium sulphate. A thermodynamic calculation shows that these side reactions will be suppressed to insignificance if the equilibrium is studied in the presence of an excess of hydrogen. The apparatus used is shown in Fig. 1. About 10 g calcium oxide and 20 g calcium sulphide (laboratory qualities) were intimately mixed, and some water was added to make a thick paste. The paste was put into a thimble of zirconium silicate, which was placed within the constant temperature zone of a furnace, and capillary refractory tubes were attached in both ends. After the mixture had been heated in dry hydrogen at 1000°C for several hours all Ca(OH), and CaCO, had decomposed and CaSO, was reduced, so only CaO and CaS remained in the thimble forming a porous plug. The mixture was examined by X-ray diffraction after the initial reduction in dry hydrogen as well as after the subsequent experimental runs up to 1425 °C. It was shown that crystalline calcium oxide and calcium sulphide were always present together in about equal amounts. The unit cell edges were found to be 4.80A for CaO and 5.68A for CaS in good agreement with existing literature values." This shows that the mutual solid solubility is very small, and that the compounds are present in their standard states. Purified hydrogen was passed through water sat-urators kept at constant temperature in a thermostat bath. The amount of water vapor saturation was checked by means of a dew point method, not shown on Fig. 1. The gas mixture was passed through the capillary inlet into the furnace, where it was sifted through the porous plug of calcium oxide and calcium sulphide. The hydrogen sulphide present in the outgoing gas was absorbed in a zinc acetate solution and the hydrogen was collected over water. When one liter of hydrogen had been collected, the amount of hydrogen sulphide was determined by iodometric titration. As one molecule of H,O is used for the formation of each molecule of H,S, the equilibrium ratio H,S/H,O would be , where (H,O) is the molar concentration in the ingoing gas, and (H,S) the molar concentration in the outgoing gas. In the present work (H,S) was always very small compared to (H20). In order for the observed H,S/H20 ratio to represent the true equilibrium ratio the gas flow has to be: 1—Sufficiently slow to give a complete establishment of equilibrium, and 2—sufficiently fast to counteract thermal diffusion. Incomplete reaction would give a value decreasing with increasing flow rate, and thermal diffusion would give a value increasing with decreasing flow rate. When inlet and outlet tubes of about 2 sq mm cross-section were used, the observed gas ratio was independent of the flow rate between 15 and 125 cc per min, Fig. 2. In this range, therefore, the observed gas ratio represents true equilibrium.* For the rest of the in-

Jan 1, 1952

By G. Krauss, W. Pitsch

The fine structure of the bcc martensite formed in an Fe-33 wt pct ATi single crystal of arrstenite is sho~on by transmission electron microscoPy to consist of combinations of transformation twins, stacking faults, deformation twins, and regular arrays of parallel screw dislocations. These structures constitute evidence for the multiple lattice-invariant deformations which operating during the formation of martensite could produce the real habit-plane scatter measured by a two-surface analysis of the plates formed in the single crystal of this investigation and reported in the literature for other Fe-Ni rnartensites. CRYSTALLOGRAPHIC theories1,2 of martensitic transformation show that the habit plane of martensite in a parent lattice is dependent in part upon an inhomogeneous distortion or lattice-invariant deformation which takes place on a fine scale within a martensite plate during its formation. Several recent theoretical papers3,4 have addressed themselves to an analysis of a wide variety of conceivable lat-tice-invarient deformations and the habit planes which they produce, while experimental investigation have been concerned with either the measurement of habit planes or the description and identification of the martensitic fine structure which reflects the nature of the lattice-invariant deformation operating during transformation. In Fe-Ni alloys with subzero Ms temperatures, the group of alloys with which this paper concerns itself, habit planes have often been found to scatter an amount greater than might be expected from possible experimental errors,5-7 and fine twinning has been identified as a major constituent of the fine structure of martensite.8-11 It has been suggested3,4 that more than one type of invariant shear occurs during martensitic transformation. This possibility has been experimentally supported12,13 by the observation of both dislocation configurations and twinning in a single martensite plate. The purpose of this paper is to report additional evidence for multiple lattice-invariant deformations in martensite and so to account for the real scatter in the habit planes of the martensite plates formed in Fe-Ni alloys. EXPERIMENTAL PROCEDURE The Fe-Ni single crystal was produced by pulling a high-purity iron and nickel charge through a single-crystal vacuum furnace in an alumina crucible. The crystal was double-melted to promote homogeneity and to increase its size by further additions on the second pass. In its final form the crystal was 4 cm in diam and 5 cm long. The nickel and carbon contents were analyzed at 32.9 and 0.006 wt pct, respectively. The austenite of this alloy first transformed to martensite by bursts at about -120°C, and, to preserve as much of the austenite as possible, all transformation was performed just below -120°C. Some observations were made on transformed samples which had been heated for 2 min at 340°C. It is assumed that the features of the martensite of these samples, Figs. 1 and 4, are the same as those of the as-quenched martensite. Orientation of the crystal by X-ray diffraction established 10.735 0.609 0.3161? as the axis of the crystal, an orientation that was checked within 2 deg by neutron diffraction. Further checks by electron diffraction of samples cut normal to the axis confirmed this orientation within the larger limits of error inherent in electron diffraction of thin foils. The X-ray orientation was the one used for the two-surface analysis of the martensite habit planes. A two-surface analysis was performed on the quadrant of the single crystal which had been oriented by both X-ray and neutron-diffraction techniques. Photomicrographs at X50 were made on two surfaces along an edge 2 cm long. Fiducial marks and the fact that many of the plates were almost completely surrounded by retained austenite made good matching of individual plates on two surfaces possible. The habit-plane trace on a surface was taken as the best line parallel to the long axis of a plate. A measure of the accuracy afforded by this criterion was provided by a family of very large plates which appeared at intervals along the entire 2 cm length of the edge. The plates all had habit-plane traces within 2 deg of one another. Many of the plates did not show midribs and, therefore, the use of midribs7 to represent habit-plane traces was not feasible in this investigation. The over-all experimental accuracy is estimated to be better than ±2 deg. Samples for transmission examination in a Siemens Elmiskop I at 100 kv were prepared by cutting 2-mm-thick discs from the single crystal, removing about 0.5 mm by chemical polishing,14 trans-

Jan 1, 1965

By H. Conrad, V. Damiano, J. Hanafee, N. Inoue

The effects of hydrostatic pressure up to 400 ksi at 25" to 300°C on the mechanical properties of three forms of commercial beryllium (hot-pressed block, extruded rod and cross-rolled sheet) were investigated. Three effects of pressure were studied: mechanical beharior under pressure, the effect of pressure-cycling, and the effect of tensile prestraining under hydrostatic pressure on the subsequent tensile properties at atmospheric pressure. For all three materials the ductility increased with pressure whereas the flow stress did not appear to be significantly influenced by pressure. An increase in the subsequent atmospheric pressure yield strength generally occurred as a result of pressure-cycling or prestraining under pressure, whereas either no change or a decrease in ductility occurred. The only exception to this was sheet material, which exhibited some improvement in ductility following a pressure-cycle treatment of 304 ksi pressure. The effects of pressure-cycling and prestraining were relatively independent of the temperature at which they were conducted. Stabilized cracks of the (0001) type were found in hot-pressed specimens and {1120) type in extruded and sheet specimens following straining under pressure. Also, pyramidal slip with a vector out of the basal plane, presumably c + a, was identified by electron transmission microscopy for extruded rod and for sheet strained under pressure. Small loops similar to those previously reported were found after straining at pressures of the order of 300 ksi. THE use of beryllium in structures is limited because of its poor ductility under certain conditions. Therefore, one objective of the present research was to determine if the ductility of beryllium at atmospheric pressure could be improved by prior pressure-cycling or prestraining under hydrostatic pressure. Another objective was to study the mechanisms associated with the plastic flow and fracture of the polycrystalline form of this metal with pressure as an additional variable. Since the early work of Bridgman,1 it has been recognized that many materials which are brittle at atmospheric pressure exhibit appreciable ductility when strained under high hydrostatic pressure. This effect has been reported for beryllium by Stack and Bob-rowsky2 and by Carpentier et al.3 and has been attributed to the operation of pyramidal slip systems with slip vectors inclined to the basal plane while cleavage or fracture is suppressed.4 That such slip may occur simply by the application of pressure alone without external straining (pressure-cycling) is suggested by the results on polycrystalline zinc5 and polycrystalline beryllium,6 where nonbasal dislocations with a vector (1123) were reported. A significant improvement in the ductility of the bee metal chromium by pressure-cycling has been reported.7 On the other hand, limited studies on the pressure-cycling of the hcp metals zinc67819 and beryllium6 indicated no improvement in ductility; there only occurred an increase in the yield and ultimate strengths. The study on beryllium was limited to hot-pressed material. Consequently, additional studies on the effects of pressure-cycling on other forms of beryllium seemed desirable, especially since for chromium some authors10 have been unable to detect any improvement in ductility while others find a large improvement.7 That the ductility of polycrystalline beryllium at atmospheric pressure might be improved by prior straining under hydrostatic pressure was suggested by the known beneficial effects of cold work on the ductile-to-brittle transition temperature in the bee metals. It was reasoned that, by straining under hydrostatic pressure, fracture would be suppressed, and during the propagation of slip from one grain to its neighbor dislocations with a vector inclined to the basal plane"-'4 would operate. Upon subsequent straining at atmospheric pressure, these dislocations with a nonbasal vector would continue to operate and thereby reduce the tendency for fracture to occur, by assisting in the propagation of slip across grain boundaries and by interacting with any cracks that may develop. It was recognized that maximum improvement in ductility would probably occur at some optimum amount of prestrain under hydrostatic pressure. If the pre-strain was too small, an insufficient number of dislocations with a nonbasal vector would be activated; if it was too large, internal stresses (work hardening) might increase the flow stress more than the fracture stress, or incipient cracks or other damage could develop. EXPERIMENTAL PROCEDURE 1) Materials and Specimen Preparation. The materials employed in this investigation consisted of hot-pressed block (General Astrometals, CR grade), extruded rod (General Astrometals, GB-2 grade with a reduction ratio of 8:1), and cross-rolled sheet (Brush S200, 0.065 in. thick). The analyses of these materials and mechanical properties at room temperature and atmospheric pressure are given in Table I. The grain size of the hot-pressed block was 15 to 16 µ, that of the extruded rod 10 to 11 µ, and that of the sheet 7 to 10 µ in the rolling plane and 5 to 6 µ in the thickness, all determined by the linear intercept method. Al-

Jan 1, 1969

By Pradeep K. Rohatgi, Clyde M. Adams

Structures produced upon solidification of the eu-tectic composition (33 wt pct Cu) aluminum copper alloy have been examined as a function of freezing rate dfs /d? , the rate of change of fraction solid (fs) with time (8). Slow (dfs/d? = 0.0016 sec-1), intermediate (dfs/d? = 0.02 sec-1) and rapid (dfs/d? = 0.4 to 7.30 sec-1) freezing rates were used. The lamellar Al-Cual2 eutectic is arranged in the form of rod-shaped colonies at rapid freezing rates. The colonies are aligned parallel to the direction of heat flow, whereas the lamellae within the colonies are aligned at various angles, as high as 90 deg, to the direction of heat flow. The colony spacing (C) is proportional to the square root of inverse freezihg rate. The relationship is C = 15.5(dfs/d?)-1/2 where C is in µ and 8 is in sec. The ratio of colony spacing to lamellar spacing is greater than 20.0 and increases with a decrease in the freezing rate. A duplex dendritic structure is produced at intermediate freezing rates. A fine lamellar eutectic is arranged within the dendrites (exhibiting side branches at an angle close to 60 deg from the main stem) and a coarse irregular eutectic appears in the interdendritic regions. The duplex eutectic structure is also produced at slow freezing rates. However, at slow freezing rates there is a Platelat of CuAl2, along the center of the main stem of each dendrite and the other lamellae are arranged perpendicular to the central platelet. THE eutectic between CuA12 and a! aluminum has been reported to freeze in a lamellar form by several workers.'-3 chadwick4 has measured the interlamel-lar spacing as a function of growth rate. Kraft and Albright2 have reported on irregularities in the lamellar structures, and have proposed growth models which account for the formation of faults during solidification. In certain instances the lamellar eutectic has been found to exist in colonies. The colony formation315 has been attributed to the breakdown of a planar liquid-solid interface due to rejection of impurities. The aim of the present work is to study the structures produced from the eutectic aluminum-copper alloy under relatively fast solidification rates, such as encountered in casting and welding operations. The solid-liquid interface presumably remains planar under conditions of slow unidirectional freezing which produce lamellae aligned parallel to the direction of heat flow. The local growth velocities are the same over the entire interface and are equal to the rate of growth of the all-solid region. The spacing between the eutectic lamellae is inversely proportional to the square root of the growth rate of the all-solid region. Under the freezing conditions used in the present study, the solid-liquid interface is cellular or dendritic and the local growth velocities are different in the different regions of the interface. The relationship between the growth rate of the all solid region and the local growth velocities varies with the location and the shape of the interface. The growth rate of the all-solid region is, therefore, an inadequate parameter to describe the eutectic micro-structures which depend upon the local growth velocities. For this reason the structures have been examined as a function of freezing rate, dfs/d?, where fs is the fraction solidified at time 0. The freezing rate was varied by a factor of 4000. The relationship between the freezing rate, dfs/d?, and the growth velocit of the all solid region depends upon the specimen geometry and the shape of the interface. EXPERIMENTAL PROCEDURES The A1-33 pct Cu alloy used throughout this study was made in an induction furnace, using electrolytic copper and aluminum of commercial purity (99.7 pct), the primary impurities being silicon (0.12 pct), iron (0.14 pct), and zinc (0.02 pct). Three ranges of freezing rates were investigated: 1) A spectrum of rapid freezing rates (ranging from 0.40 to 7.30 sec-1) was obtained in arc deposits made on 2-in. thick cast plates of the eutectic alloy. The arc was operated at constant power and was made to travel at constant velocity on the surface of the plate that was in contact with the chill surface during solidification. The pool of liquid metal formed under the moving tungsten arc solidified rapidly by heat extraction through the unmelted plate. Conditions of unidirectional heat flow were achieved near the fusion zone interface, especially in the center of the arc deposits. The great advantage of the arc technique is that rapid cooling and freezing rates can be varied in a qualitative way. The correlation between the arc parameters and the solidification rate is given by the following relationship:6-8

Jan 1, 1970

By N. C. J. Ros

The paper deals with pressure gradients occurring in flowing and gas-lift wells, a knowledge of which can be applied to the determination of optimum flow-string dimensions and to the design of gas-lift installations. The study is based on a pressure-balance equation for the pressure gradient. It appears that a pressure-gradient correlation of general validity must essentially consist of two parts-—one part being a correlation for liquid hold-up and the other part being one for wall friction. Dimensional analysis indicates that both liquid hold-up and wall friction are related to nine dimensionless groups. It is shown that in the field of interest only four groups are really important. On the basis of these four groups a restricted experimental program could be selected that nevertheless covered practically all conditions encountered in oil wells. This experimental program has been carried out in a laboratory installation. Three essentially different flow regimes were found. The pressure gradients in these regious are presented in the form of a set of correlations. Comparison of these correlations with a few available oilfield data showed excellent agreement. INTRODUCTION Prediction of the pressure drop in the flow string of a well is a widely known problem in oilfield practice. Accurate data on the pressure gradient of a simultaneous flow of gas and liquid in a vertical pipe are especially useful for the determination of optimum flow-string dimensions. It is well known that with moderate gas and liquid flows such a vertical string acts as a "negative restriction". The pressure drop decreases (1) when the throughput through a given pipe increases, and (2) when at a given throughput the cross-sectional area is decreased. The reason is that, with increasing velocities, the flow becomes more agitated so that the gas slips relatively more slowly through the liquid. With the resulting increase in gas content in the string, the static head decreases. When the area becomes very small, however, the high velocities entail great wall friction, which causes an increase in pressure drop. For a given flow, therefore, minimal pressure drop is obtained by using a certain cross section. This means that, in principle, each well can be provided with an optimum flow string for minimum pressure drop and, hence, maximum possible production rate. The procedure for the selection of the optimum string has been discussed by Gilbert.' A necessary tool in the procedure, however, is accurate knowledge of the pressure gradient to be expected for various values of the governing variables. Another application of pressure-gradient data lies in the field of gas-lift practice: they provide a means of determining the optimum gas-injection rate, optimum injection pressure and optimum injection depth. Much work has already been done in the study of the pressure gradient of vertical gas-liquid flow. Poett-mann and Carpenter2 presented a pressure-gradient correlation based on measurements in wells. This correlation has been found to provide accurate predictions in high-pressure wells and in high-production wells for flow through both tubing and annuli.2-5 However, when their method is checked on low pressure-low production wells or on wells with viscous crudes, serious discrepancies are found. As we shall see in the next section, this is due to the fact that their correlation factor, representing all irreversible energy losses, is given as a function of only one correlation group. Some important variables, such as gas-liquid ratio and liquid viscosity, are not incorporated in this group so that their specific effects are not accounted for. To study also the mechanism of vertical gas-liquid flow outside the ranges covered by the Poettmann-Carpenter publication and extensions, a laboratory investigation has been carried out. This study is founded on a pressure-gradient equation that is based on a pressure balance. To reduce the number of test runs required, a dimensional analysis has been carried out, followed by a selection of relevant dimensionless groups. These groups guided a subsequent experimental study, and with their aid the experimental program could be minimized while still covering the majority of the situations encountered in oilfield practice. In this paper the choice of a formula for the pressure gradient is discussed first. This is followed by a brief description of the experimental setup. Subsequently, the dimensional analysis is discussed and the relevant dimensionless groups are selected, resulting in the experimental program required. The general relationships of pressure gradient and liquid hold-up are then described; various flow patterns and a certain flow instability (so-called "heading") are discussed and a set of correlations is presented which shows a good agreement with the measurements and a few available field

By W. Bonfield

The temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of polycrystalline Cu 1.9 wt pct Be have been measured for the solution treated condition, an intermediate condition containing G.P. zones and ?' precipitate and the overaged ? precipitate condition, in the range from -58° to 200° C. A transition in micro -yield behavior and a large temperature dependence were noted for the intermediate condition, which are interpreted in terms of the interaction of glide dislocations with two differently sized zones. In comparison the microscopic yield stresses of the solution treated and overaged conditions were less sensitive to temperature variations and are satisfied by the Mott-Nabarro and dislocation bowing theories, respectively. A determination of the temperature dependence of the yield stress of a precipitation hardening alloy has provided a powerful tool for evaluation of the operative deformation mechanism. There is a marked contrast between the effect of temperature on the yield behavior of a metal containing coherent zones or intermediate precipitates, which can be "cut through" by mobile dislocations, and a metal containing a dispersion of noncoherent particles, through which dislocation "bowing out" is the dominant role of deformation.' These studies have in general been confined to single crystals, as it was considered that similar experiments on polycrystalline material did not produce good data because of the lack of sensitivity with which the yield stress could be determined. However, this objection has been removed by the introduction of mi-crostrain techniques, with which the yield stress in polycrystalline materials can be measured to a strain sensitivity of 10-6. Such measurements have not only shown that the deformation of polycrystalline precipitation hardening alloys can be examined with the same detail as single crystals, but also that some unexpected results are obtained.' In this paper the results obtained from a study of the temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of a polycrystalline Cu 1.9 wt pct Be precipitation hardening alloy (Berylco 25) are discussed. The temperature dependence of the alloy was measured for three different conditions: 1) The solution treated condition (a supersaturated solid solution of a containing ~12 at. pct Be3) which is obtained by water quenching the alloy from 800° C. 2) The condition of y' intermediate precipitate, to- gether with some G.P. zones,' which is produced after an aging treatment of 2 hr at 315°C from the solution treated condition. (The alloy was cold rolled to 40 pct reduction prior to aging to minimize grain boundary precipitation effects.)4 3) The condition with equilibrium ? precipitate structure2 which is developed after an aging treatment of 24 hr at 425° C. EXPERIMENTAL PROCEDURE Tensile specimens of gage length 1 in. and with rectangular cross section of 0.18 by 0.06 in. were prepared from the solution treated, cold rolled alloy and were either resolution treated for 1 hr at 800°C, followed by water quenching, or aged for 2 hr at 315°C and 24 hr at 425° C to produce the desired precipitate structures. The microstrain characteristics of the aged specimens were determined at temperatures from —58" to 200° C and those of the solution treated specimens from -58° to 30° C. Each temperature was controlled to ± 0.2°C, which was a level of stability sufficient to eliminate thermal expansion effects from the measurements (~1.2°C temperature increase produced an extension of 2 x 10-6 in.). The microplastic behavior of the specimens in the temperature range below 82" C was measured with a standard Tuckerman strain gage,5 while at temperatures above 82°C a modified Tuckerman gage with a reduced strain sensitivity (4 x10-6 in. per- in.) was used. A load-unload technique was used to establish values of the microscopic yield stress. The specimen was strained at a constant cross head speed of 2 x 10-2 in. per min to a given stress level, at which the total strain was measured. Then the specimen was immediately unloaded at the same rate and any residual plastic strain determined. This procedure was repeated for an increasing series of stress levels until the microscopic yield stress was established by a direct measure of the stress to produce a residual plastic strain of 2 x 10-6 in. per in. (It should be noted that, as reversible dislocation motion occurs at stresses less than the microscopic yield stress,2 the plastic strain rate at this level was not constant.) In an ideal test, the microscopic yield stress would be determined from a continuous stress-strain measurement, rather than from a load-unload sequence, in order to eliminate mechanical recovery effects.6 However, it was found experimentally that mechanical recovery was negligible in Cu 1.9 wt pct Be at small plastic strains for all the temperatures investigated, as the microscopic yield stress was independent of the number of load-unload cycles employed (i.e., the values measured for specimens subjected to different numbers of cycles was within the experimental scatter determined for specimens tested in an identical manner). Therefore, it is reasonable to consider the microscopic yield stress determined in the load-unload

Jan 1, 1969

By K. H. Hiller

A rotational viscometer has been designed which perrnits the measurement of the rheological properties of drilling muds and other non-Newtonian fluids under conditions equivalent to those in a deep borehole (350F, 10,000 psi). The important mechanical features of this instrument are described, and its design criteria are discussed. The flow equations for the novel configuration of the viscometer are derived and the calibration procedures are described. The data and their interpretation, resulting from measurement of the flow properties and static gel strengths of homoionic montmorillonite suspensiom at high temperatures and pressures, are presented. Data are also presented for the flow behavier of typical drilling fluids at high temperatures and pressures. The pressure losses in the drill pipe and the annulus depend critically upon the flow parameters of the drilling fluid. This work demonstrates the need to measure these parameters under bottom-hole conditions in order to obtain a reliable estimate of the pressure losses in the mud system. INTRODUCTION The rheological properties of drilling fluids are affected by temperature and pressure, but the extent of these effects on the dynamic flow properties is not well known. Measurements of changes of the flow properties of clay-water drilling muds with temperature have been reported by Srini-Vasan and Gatlin.1 The temperatures reported did not exceed 200F, a limitation imposed by the apparatus used by these authors. The rheological properties of clay suspensions were measured at temperatures up to 100C by Gurdzhinian.' Neither the nature of the exchange ions in the clay suspensions nor the degree of purity were defined in his work, nor were the measurements extended to currently used drilling fluids. The lack of systematic measurements of dynamic flow properties at high temperatures and pressures seems the more surprising since during the last decade the importance of the control of the hydraulic properties of drilling fluids has come to be widely recognized. Very good mathematical treatments of the friction losses in drill pipe and annulus have been developed.3 4 These treatments are based on the assumption that drilling fluids behave as Bingham plastic fluids. Quite often this assumption is justified, while in other cases a power law equation pro- duces better fit than the Bingham model does. For convenience in applying viscometer data to pressure-drop calculations, the Bingham plastic flow equation is preferable and, therefore, has been applied to the data reported in this paper, although other equations may fit these data more accurately. In a Bingham plastic fluid the relationship between the shearing stress 7 and the rate of shear D is given by the following equation: where is the plastic viscosity and 4 the yield point. If 4 = 0, the equation for simple Newtonian flow, 7 = pD, is obtained. Two empirical constants are required for the description of laminar flow of a Bingham plastic fluid, and calculations of the flow behavior at high temperatures and pressures cannot be better than is permitted by the accuracy with which these constants are known. For this reason a high-pressure, high-temperature rhe-ometer has been designed to measure the plastic viscosity the yield point +, and the static gel strength S, at pressures up to 10,000 psi and temperatures up to 350F. The important features of its design will be described. The results of measurements on homoionic clay slurries will be discussed insofar as they are relevant to an understanding of the general flow behavior of clay-water drilling fluids. The results of measurements on some typical drilling fluids will be presented also, and their practical implications will be briefly discussed. DESCRIPTION OF EQUIPMENT MECHANICAL FEATURES A viscometer designed to measure the plastic viscosity, yield point and gel strength of non-Newtonian fluids must permit the measurement of the shearing stress t at any given rate of shear D. This is possible only if t and D are approximately uniform throughout the entire sheared sample. A Couette apparatus is the most convenient method of realizing this condition, as has been pointed out by Grodde." The "high-pressure, high-temperature rheometer" described in this paper is basically a rotational Couette viscometer that is immersed in a cell in which pressure and temperature can be controlled over the range of interest. Fig. 1 shows schematically the important features of the pressure cell and associated equipment. The heart of the instrument is the rotating cup. It is shown more clearly in Fie. 2. which revresents the lower one-third of the pressure cell (below the input drive shaft shown in Fig. 1), and it is shown in detail in Fig. 3. For measurements of dynamic flow properties, the rotating cup is driven by a 1/2-hp electric motor, which operates through a Vickers

By K. Tangri, B. Swaroop

Simultaneous measurements of lattice (elastic) strain by X-ray line shift method and total strain with an electrical strain gage have been carried out on polycrystalli,ne nickel with the help of a specially designed tensometer attachment for the X-ray dif-fractometer. During the initial stages of deformation, the rate of increase in lattice strain closely follows the total strain until the plastic strain sets in. From then onwards, the two strains deviate from each other and with further increase in afiplied stress the rate of increase of lattice strain eventually decreases. Depending upon the mode of unloading, both compressive and tensile strains have been observed in nickel deformed up to 0.29 pct strain. These results have been explained on the basis of the effects of clustering of dislocations and also the production and behavior of point defects during loading and unloading, respectively. POLYCRYSTALS deformed plastically in a uniaxial tension test show residual lattice strains (hereafter referred to as RLS), which broaden the X-ray line profiles and shift their peak positions.''4 It is known that uniform straining of a crystal lattice (macrostrain) produced movement of ddfraction line peaks, whereas nonuniform straining (microstrain) causes line broadening.= Though the nature and origin of RLS in deformed metals is not yet clearly understood, these are believed to be due to the presence of some form of a locked-up stress system. Several possible detailed interpretations6'" of the stress system have been proposed by various workers and common to all these interpretations is the assumption that different parts of the aggregate have different tensile yield stresses; e.g., that a part A yields under a lower applied stress than a part B. Therefore, during the deformation process, the elastic strain in A will be less than that in B, and, after completion of deformation, B will tend to contract further than A but will be prevented from doing so by the restraining influence of A. Thus, when equilibrium is reached, A will be in compression while B is in tension. Although there is general agreement on the correctness of this argument, controversy still exists as to the exact nature of the parts A and B in a deformed metal. In an alternative approach to the creation of parts A and B, many other investigators have assumed that the RLS observed in unloaded specimens are in some way connected with the lack of proportionality between lattice strain and applied stress in the region above the yield stress." cullity13 has prepared a schematic summary of the results of previous workers, mainly Smith and Wood,2'11 which suggests that, above the elastic limit, the lattice strain may increase less rapidly with respect to strain, or may even decrease with increase in applied stress. If the applied stress is then decreased, the lattice strain would decrease along a line parallel to the loading line in the elastic region and thus produce a compressive residual lattice strain after unloading. At equilibrium, to balance these compressive stresses? there would have to be regions under tensile stress which may well be the grain boundaries or the substructure walls formed during deformation. The present investigation was undertaken to gain a better understanding of the nature and origin of RLS and also to experimentally verify the salient features of this hypothesis. EXPERIMENTAL Stress and strain determinations were made with a specially constructed tensometer attachment for the X-ray diffractometer, Fig. 1: which permits the following measurements simultaneously on a sheet specimen under uniaxial tension at various stress levels during loading and unloading: a) lattice strains, E=. in a direction perpendicular to the direction of pulling (x direction) from shifts in X-ray line peak positions; b) the total strain, ex, in the direction of pulling. with the help of an electrical strain gage affixed to the back of the specimen directly below the area irradiated by X-rays: and c) the applied stress, with the help of a load cell which consisted of a calibrated stainless-steel sample of dimensions identical to those of the specimen under investigation, and to which it was coupled. Because of its high stacking fault energy.I4 nickel

Jan 1, 1970

By T. E. Leontis

Data are presented in this paper to show that addition of zirconium to sand-cast Mg-Th alloys effects a marked decrease in the grain size of these alloys which is accompanied by a significant increase in the mechanical properties over the entire range of thorium content investigated. The beneficial effect of zirconium on the strength properties is maintained at elevated temperatures up to 700°F. In addition the alloys exhibit exceptionally high creep resistance at temperatures up to 600°F. Zirconium does not greatly improve the strength or creep characteristics of extruded Mg-'Th alloys. Cerium is not a desirable addition to Mg-Th-Zr alloys. IN a previous paper,' it was shown that addition of thorium to magnesium imparts exceptionally high resistance to creep at elevated temperatures both in the sand-cast and in the extruded states. The large grain size of the sand-cast alloys, however, renders them of questionable value as engineering materials. Sauerwald² showed that the grain size can be reduced effectively by the addition of zirconium. Results of a detailed study of the properties of Mg-Th-Zr alloys over a wide range of thorium content are presented in this paper. In accordance with the preliminary findings of Sauerwald,² it is shown here that Mg-Th-Zr alloys possess the unusual combination of fine grain size and a high level of strength and creep resistance at elevated temperatures. Some information on the effect of cerium on the properties of Mg-Th-Zr alloys is presented also. Effect of Th on Solubility of Zr in Molten Mg Sand-cast test bars and 3 in. diam extrusion billets of Mg-Th-Zr and Mg-Th-Ce-Zr alloys* were pre- pared according to the procedures described in the previous paper.' The zirconium was added in the form of sponge metal as supplied by the Bureau of Mines.' The maximum amount of zirconium that usually can be introduced into magnesium at the customary alloying temperature of 1350° F is about 0.7 pct. The analyses in Table I clearly show that thorium in- creases the solubility of zirconium in liquid magnesium. The tabulated zirconium contents are designated as "acid soluble;" this serves to distinguish these values from the small amount of zirconium that is not dissolved when the alloy is subjected to the action of a dilute acid solution. The "acid-insoluble" zirconium is believed to be ineffective as an alloying ingredient. The acid-insoluble zirconium contents ranged between 0.03 and 0.16 pct in the present alloys, the tendency was toward higher values in alloys with higher thorium content. In contrast to the effect of thorium, cerium decreases the solubility of zirconium in magnesium. This is shown by the three Mg-Th-Ce-Zr alloyst in- cluded in Table I and stands in agreement with the observations of Nelson and Stricter".' on Mg-misch-metal-Zr alloys. Effect of Zr on Grain Size of Mg-Th Alloys The potent effect of zirconium as a grain refiner has been demonstrated for many types of magnesium alloys.3-8 Of greatest importance to date are Mg-Zn-Zr alloys5,6,8 and Mg-mischmetal-Zr alloys.3,4,7 Zirconium has also been found to exert a marked grain-refining action on Mg-Th alloys. All the Mg-Th-Zr alloys cast in the form of ½ in. diam test bars have an exceedingly fine grain size (Table I). Reference to the previous paper' will show that binary Mg-Th alloys containing up to 6 pct Th are almost completely columnar even in the M in. diam reduced section of a test bar, and that 10 to 50 pct Th alloys have an equiaxed grain structure of 0.03 to 0.08 in. The data in Table I also show that addition of cerium to Mg-Th-Zr alloys has no effect on the grain size. In addition to increasing the strength properties, the fine grain size of Mg-Th-Zr alloys

Jan 1, 1953

By J. J. Gilman, T. A. Read

FOLLOWING the deformation 01 zinc monocrys-tals, sharply bent basal planes are observed near several types of inhomogeneities. Three of these in-homogeneities have characteristics which are quite regular so that they can be studied and analyzed. These are compressive kink bands, "deformation bands," and the inhomogeneities near end restraints. The present paper describes experiments in which "deformation bands" were artificially produced, and bend plane phenomena are discussed in terms of dislocation theory. Also, two new bend plane phenomena are described. The importance of bend plane phenomena in the deformation of crystals is not widely recognized. Many phenomena may be explained in a manner similar to the discussion in this paper. Jillson1 has pointed out that the "punching effect" in zinc is a bend plane phenomenon and is not caused by prismatic slip.' Bowles3 has suggested that they may be involved in diffusionless phase changes. Cahn4 has discussed the role of bend plane formation in the polygonization of zinc. Experimental Work Tensile Kink Bands: Because of the geometrical similarity between "deformation bands" and "kink bands" (compare Fig. 1 of this paper with Fig. 1 of the paper by Hess and Barrett"), the band shown in Fig. 1 of this paper will be called a "tensile kink band," and that shown by Hess and Barrett will be called a "compressive kink band." It is felt that the term "deformation band" should be reserved for banded structures in polycrystalline materials such as iron." Tensile kink bands seem to form spontaneously in aluminum crystals deformed by tensile loading.7-10 In zinc and cadmium crystals they do not form in good, carefully loaded specimens.'." However, tensile kink bands can be produced artificially in zinc crystals. The present authors did this by scratching one of the flat surfaces of triangular crystals transversely with a sharp needle. Natural tensile kink bands caused by inhomogeneities sometimes appeared in deformed crystals which were identical in appearance with the artificially produced ones. Zinc monocrystals were grown by the Bridgman method in graphite molds. Chemically pure zinc (99.999+ pct Zn) was used and the molds were sealed inside evacuated pyrex tubes during growth. The crystal cross sections were equilateral triangles with a typical base of 0.210 in. The artificial kink band shown in Fig. 1 is typical of tensile kink bands in zinc. The band lies between two bend planes which run from upper right to lower left and is inclined oppositely to the slip bands which are sharply bent at the two bend planes. The general form of the artificial tensile kink bands was independent of the scratch depth (1 to 5 mils deep) and also independent of which side was scratched. These variables did cause variations, however. Deep scratches produced more localized kink bands than light scratches. Also, if the angle between the slip plane traces and a transverse scratch varied appreciably among the three sides, then localization of the resulting kink bands also varied. Furthermore, if the slip direction lay nearly parallel to the scratched side, the band was more developed near the scratched side than at the opposite edge. Scratches produced tensile kink bands for crystal orientations from xo = 15" to x, = 75". Fig. 2 shows a scratched crystal after deformation. One triangular side lies in the plane of the photograph. The right hand tensile kink band was produced by a transverse scratch on the upper right side. The next two kink bands were the result of scratches on the front surface. The kink band at the left was caused by a scratch on the lower back side. All four bands have the same general form. A longitudinal scratch was also made on the crystal shown in Fig. 2 to determine the effect of a scratch on the critical shear stress. The critical shear stress of the scratched region was 33.9 g per sq mm compared to 24.4 g per sq mm for the un-scratched region above it. Fig. 3 shows Laue patterns of the crystal shown in Fig. 2. Fig. 3a shows the pattern of the undeformed crystal. The orientation was x, = 21°, A, = 31". After deformation, Fig. 3b was made of the homogeneously deformed portion of the crystal. The spots are compact but split into two halves. This region was elongated 45 pct and its orientation was x = 14", X = 20"; the sine law predicts x = 14", A = 20.5". Fig. 3c was taken near the center of the middle tensile kink band of Fig. 2. The pattern shows a range of orientations and polygonization in this region. The spread in orientation was due to the fact that the basal planes were curved (see Fig. 1) rather than flat as in the ideal case. Some may also have been the result of elastic distortions and "local curvatures." The orientation range was x = 23" to 32", A = 30" to 42". It is apparent from Fig. 3 that the material inside and outside the kink band rotated in opposite directions with respect to the tension axis during deformation. The orientation calculated from the ideal configuration of Fig. 9,

Jan 1, 1954

By C. W. Kovach, A. Moskowitz

Studies were undertaken to investigate the effects of manganese content on the machinability and other Properties of a free machining martensitic stainless steel (AISI Type 416). Machinability was found to be significantly improved in steels of high manganese content, and a direct relationship was obtained between machinability and steel Mn:S ratio. As the manganese content of the steel increases, the sulfide Phase present changes from CrS to (FeMn)Cr2S4 to (MnFeCr)S, and finally to MnS. The average sulfide inclusion hardness decreases through the same range of increasing manganese content. The mechanism for machinability improvement is discussed in terms of a soft ductile sulfide affecting deformation in the secondary shear zone. Type 416 containing relatively high manganese for improved machinability shows good general properties. The effects of increasing manganese content on mechanical properties, cold formability, and corrosion resistance are described. THE addition of sulfur is commonly used to improve the machinability of stainless steels. However, little attention has been paid in the past to the composition and characteristics of the sulfur-containing phase or phases present in these resulfurized steels. Recent information on the properties of sulfide phases, and their role in metal cutting, suggests that variations in these phases could have critical effects on machin-ability, as well as important effects on formability and other properties such as corrosion resistance. Manganese, chromium, and iron are strong sulfide forming elements present in stainless steels! of these, manganese has the greatest sulfide forming tendency and iron the least.1"1 The manganese content of resul-furized 13 pct Cr steels, often about 0.5 pct, can be insufficient or only barely sufficient to combine with the sulfur that is present; thus, the precise level of manganese can strongly influence the nature of the sulfide phase. Sulfide phases which may be present in stainless steels have been reported to include CrS, a spinel-type sulfide, chromium-rich manganese sul-fide, and manganese Sulfide.5,6 Detailed phase relationships for the Fel3Cr-Mn-S system have been reported by the present investigators,7 and a portion of this work will be referred to subsequently in this paper. Recent work by Kiessling6 and Chao et a1.8 has shown that sulfide phases can display wide variations in hardness, and may undergo considerable plastic deformation under isostatic loading.9-12 Early theories of metal cutting attributed the influence of sulfur to a lubricating effect. It is now apparent that the influence of the nonmetallic inclusions and their properties on crack initiation, deformation in the shear zones, and boundary films must also be considered in relation to the machining process. This paper presents the results of studies conducted to relate machinability to the various sulfide phases which occur in stainless steels. This work has led to the development of alloys with improved machinability, and has generated information on the effects of inclusions on metal cutting processes. Effects of sulfide inclusions and steel composition on other important metallurgical properties are also discussed. MATERIALS For drill machinability and inclusion studies, 10 lb laboratory heats were melted in an air induction furnace. These heats were made with sulfur contents be tween 0.10 and 0.50 pct and manganese contents be tween 0.05 and 3.0 pct. Residual elements were added to the heats in amounts typical for commercial steels. The typical compositional range covered by the heats is shown below: C Mn P S Si Ni Cr Mo Cu N 0.10 0.05 0.007 (M0 0.40 0.40 13.0 0.20 0.10 0.03 3.0 0750 The laboratory ingots were forged in the temperature range of 1800" to 2100°F to 3/4-in. sq bars, and all bars tempered to a hardness aim of 200 Bhn prior to testing. Because of differences in composition and tempering response, the tempered bars showed some variation in hardness (175 to 275 Bhn) as well as variations in delta ferrite content (0 to 50 pct). Composition, hardness, and delta ferrite content were considered in the analysis of the machinability data. Additional tests involving tool-life evaluation and determination of other properties were conducted on materials from commercially melted and processed 15-ton electric furnace heats. TESTS AND PROCEDURES Machinability of the laboratory heats was evaluated in a drill test. In this test, 1/4-in. diam holes, 0.4 in. deep, were drilled alternately in a test bar and in a standard bar for a total of four holes in each. This sequence was repeated three times using a freshly sharpened drill each time. The average time required to drill a hole in the test bar was compared to that for the standard bar. A drill machinability rating was assigned to the test bar relative to a rating of 100

Jan 1, 1970

By C. W. Mueller, P. H. Robinson

A technique was developed for depositing single -crystal films of silicon on single-crystal sapphire substrates via the pyrolytic decomposition of SiH4/H2 mixtures. Electron diffraction and X-ray Laue reflection examinations of these films revealed single-crystal patterns. These films were characterized by measuring conductivity type, thickness, resistivity, and Hall mobility. Chemical etching, dislocation staining, and electron-microscopy examination have indicated the presence of low-angle grain boundaries and microtwinning in the silicon films. The role of the sapphire substrate with respect to its quality, orientation, surface finish, and thermal and chemical treatment was investigated. Hall mobility as a function of sapphire orientation was measured. A mobility equal to 88 pct of bulk silicon mobility was attained. Insulated-gate field-effect transistors which have a transconductance of 4000 pmho at 6 ma were fabricated using these films. THE technology of the fabrication of microelectronic circuits with active and passive components directly on a single wafer of semiconductor material has attained a high degree of perfection during the last few years. One inherent difficulty with the single-wafer approach has been undesirable coupling between components arising from the common base material. Several techniques have been developed for minimizing this coupling and obtaining good electrical isolation between components; however, these result in extra capacitance being added to the circuit. The extraneous capacitance of the connecting leads, resistors, and capacitors degrade circuit performance and limit the high-frequency operation of these circuits. Recently there has been considerable interestl-3 in the deposition of silicon films upon insulating substrates. The use of silicon as the semiconductor allows the subsequent utilization of the large amount of technology which has been developed for silicon for the fabrication of good active components. A sapphire substrate supplies an excellent insulating material which at the same time gives a thermal-conductivity improvement of an order of magnitude over glass-type substrates. This paper will describe the results obtained for the deposition of single-crystal silicon layers upon single-crystal sapphire substrates as well as the characterization of these films. I) APPARATUS The 'system used for the growth of silicon films on sapphire substrates by means of the pyrolysis of SiH4/H2 mixtures is shown in Fig. 1. The all-quartz reaction chamber is water-cooled and includes a quartz optical-flat window for use in conjunction with a 5 kw, 2.5 Mc per sec constant-temperature controlled rf generator. The temperature sensor for the rf generator is a thermopile which is focused through the quartz optical flat onto the susceptor surface. With this system the rf generator will hold the temperature of the susceptor to about +0.3°C at 1200°C. The susceptor is supported on a quartz sled inclined to the gas flow to increase the uniformity of the deposition. The water jacket surrounding the reaction chamber is used to keep the quartz wall temperature low enough to limit the decomposition of the silane to the rf-heated susceptor which contains the sapphire substrates. This eliminates the reaction of silicon with the hot quartz to form SiO which deposits out on the apparatus walls, thus obscuring vision, and interferes with the optical measurements of the temperature as well as with the growth process itself. Provision is also made for "n"- and 'p"-type doping by using mixtures of either phosphine or diborane in hydrogen which are added to the silane during the growth process. The hydrogen used is the purest commercially available tank hydrogen further purified by use of a palladium diffuser. The susceptors which were used include 1) spectro-scopically pure graphite, 2) high-purity molybdenum, 3) high-resistivity silicon using a low-resistivity insert to facilitate coupling to the rf generator, 4) silicon carbide-coated graphite. The latter two susceptor materials produced silicon films on sapphire substrates with more reproducible resistivities. Prior to silicon deposition all connecting lines as well as the reaction chamber are thoroughly flushed with argon and then hydrogen. After the hydrogen flow is set, the growth temperature is adjusted to 11009 to 1150°C, and when thermal equilibrium is reached the silane flow is started. The flow rate of the hydrogen must be fast enough so that turbulent flow occurs in the size of reaction tube used, otherwise a streaked nonuniform silicon deposit occurs. After the deposition

Jan 1, 1967

By Clarence A. Seyler

The technical difficulties of cutting thin sections of coal for examination by transmitted light have hitherto restricted the investigation of the important subject of the microstructure of coal to the few possessed of the requisite skill and time. Apart from this, the method fails with anthracites and other coals rich in carbon, owing to the opacity of the material. Occasional use of the method of polishing a surface, with or without etching, has been made, but it was not until Winter' published an account of his results that attention was seriously directed to the method. In May, 1923, a specimen of dull anthracite came into my hands; I tried Winter's method on it and the presence of megaspores and other vegetable structures became clearly visible. A preliminary notice was published by me;2 but I soon abandoned the use of Schulze's solution, having found that a mixture of chromic and sulfuric acids gave far better results. In the meantime Turner and Randall, in America, had independently developed the method of flame etching, as applied to anthracite, with great success. I have spent a year studying the method of chromic etching, which gives excellent results with bituminous coals and camels, as well as with anthracite. For anthracites, I have used the chromic method and Turner's method of flame etching, whichever was the more convenient or as a check one on the other. The polishing is done, according to metallurgical practice, by the use of a polishing machine and successively finer emery paper, followed by polishing on cloth moistened with a suspension of levigated green oxide of chromium, and a final rubbing on "selvyt" (a cotton velvet polishing cloth) moistened with alcohol. The polished sample is examined by reflected light with a 2/3 and 1/6 in. objective. Bituminous coals usually show considerable structure, and even anthracites show it faintly in places. The sample is then etched by immersion in a boiling solution made by adding 10 c.c. of concentrated sulfuric acid to 30 C.C. of a saturated solution of chromic acid; enough water is then added to dissolve

Jan 1, 1925

By Michael Perch, Charles C. Russell

Nearly 95 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69,9, and in 1938 it was 61.3, To produce a net ton of pig iron 1959 lb. of coke was required in ,1940 and 1760o lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1942

By K. G. Wikle, W. W. Beaver

The factors which control the rate of dissolution of pure gold in cyanide solution were studied both directly and through measurement of solution the current-potential curves for the anodic and cathodic portions of the reaction. The mechanism of dissolution is probably electrochemical the reaction in nature, and the rate is determined by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on their relative concentrations. The significance of the results and the effects of impurities are considered. ALTHOUGH the dissolution of gold in aerated cyanide solutions has been used as an industrial process for treatment of gold ores since the late nineteenth century, the factors which determine the rate of the reaction have never been identified unambiguously. Studies of the rate of dissolution by Maclaurin,1 White,2 Christy,3 Beyers,4 Thompson,6 and others are contradictory in their conclusions; some claiming that diffusion of the reactants to the gold. surface controls the rate, and others that the chemical reaction is inherently slow and related to high activation energy for the reaction. Christy3 and 'Thompson" both suggest that the reaction is electrochemical in nature and that the dissolution of gold proceeds at local anodic regions while the oxygen is reduced at cathodic regions on the gold surface. Although their studies are ingenious and do indicate an electrochemical reaction under the conditions of study, their experiments were of limited nature and failed to identify the rate-controlling process in the system. The importance from an industrial viewpoint of a knowledge of the mechanism and rate-controlling factors in gold dissolution can be illustrated as follows: If the rate is controlled by a slow chemical reaction rather than by diffusion of the reactants, then an increased temperature should have a marked accelerating effect; agitation of the slurry should have no effect on rate: and increased concentration of reactants should cause acceleration of the rate. If the rate is controlled by the diffusion of one or the other of the reactants to the gold surface, then increased agitation should increase the rate; increased temperature will increase the rate, but not as much as for the case of a slow chemical reaction; increased concentration of the reactant which is diffusion limited will increase the rate; and the concentration of other reactants should be without effect on the rate. It may be concluded that for design of a commercial process for gold leaching, the rate-controlling factors of the reaction should be understood so that an intelligent choice of the conditions of agitation, temperature, and reactant concentration may be made. The experiments described here lead to the unambiguous conclusion that in a system of pure gold and a pure aerated cyanide solution the rate of dissolution is controlled either by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on the relative concentrations of each. There is also ample, but not conclusive, evidence that the mechanism of the reaction is identical to that of electrochemical corrosion. The practical significance of these conclusions will be discussed later in the paper. Experimental The experimental method used in this work was to employ an electrolytic cell which performed the overall gold-dissolution reaction, and to study the anodic and cathodic reactions of this cell as to their nature and the rate-controlling factors. Simple experiments on the rate of dissolution and the potential of the dissolving specimen also were performed under conditions of agitation, temperature, and concentration identical to those used in the electrode studies. Analysis of the electrode studies by well established theories of electrochemical corrosion were made, and the results were found to bear a one-to-one relation with actual rate and potential measurements. Electrode Studies: The Anodic Reaction: The gold specimen used for all of the electrode studies and the rate determination consisted of a sheet of 99.99 + pct Au wrapped around a lucite rod and sealed at the edges with plastic cement, thus forming a cylinder of gold of known and constant area (8.0 sq cm). The lucite rod was threaded into a brass spindle which could be rotated at speeds of 100, 300, and 500 rpm. For the electrode studies electrical contact between the gold cylinder and the brass spindle was made by means of a gold strip covered with plastic. The anodic dissolution of gold was studied by immersing the electrode in a solution containing known concentrations of KCN and KAu(CN)2 but free of oxygen, and by passing an anodic current through the gold electrode. The pH of the solution was maintained between 10.5 to 11.0 in these and all other tests by addition of KOH. The pH was measured before and after each test by means of a glass-elec-

Jan 1, 1955

By J. J. Tietien, R. O. Clough

A technique previously used to prepare alloys of InAs1-xPx and GaAsl-x Px, miry: the gaseous hydrides arsine and phosphine, has been extended to grow single -crystalline GaAs 1-x Sb x by replacing the phos-phine with stibine. Procedures were developed for handling and storing stibine which now make this chemical useful for vapor phase growth. This represents the first time that this series of alloys has been grown from the vapor phase. Layers of P -type GaSb and GaSb-rich alloys have been grown with the carrier concentrations comparable to the lowest ever reported. In addition, a p-type alloy containing 4 pct GaSb exhibited a mobility of 400 sq cm per v-sec which is equivalent to the highest reported for GaAs. RECENTLY, interest has been shown in the preparation and properties of GaAs1-xSbx alloys, since it was predicted1 that for compositions in the range of 0.1 < x < 0.5, they might provide improved Gunn devices. However, preparation of these alloys presents fundamental difficulties. In the case of liquid phase growth, the large concentration difference between the liquidus and solidus in the phase diagram, at any given temperature, introduces constitutional supercooling problems. It is likely that, for this reason, virtually no description of the preparation of GaAs1-xSbx by this technique has been reported. In the case of vapor phase growth, problems are presented by the low vapor pressure of antimony, and the low melting point of GaSb and many of these alloys. In previous attempts1 at the vapor phase growth of these materials, using antimony pentachloride as the source of antimony vapor, alloy compositions were limited to those containing less than about 2 pct GaSb. This was in part due to the difficulty of avoiding condensation of antimony on introducing it to the growth zone. A growth technique has recently been described2 for the preparation of III-V compounds in which the hydrides of arsenic and phosphorous (AsH3 and pH3) are used as the source of the group V element. With this method, GaAs1-xPx and InAs1-xPx have been prepared2&apos;3 across both alloy series with very good electrical properties. Since the use of stibine (SbH3) affords the potential for effective introduction of antimony to the growth apparatus, in analogy with the other group V hydrides, this growth method has been explored for the preparation of GaAs1-xSbx alloys. In addition to GaSb, these alloys have now been prepared with values of x as high as 0.8. In the case of GaSb, undoped p-type layers were grown with carrier concentrations equivalent to the lowest reported in the literature. Thus it has been demonstrated that, with this growth technique, all of the alloys in this series can be prepared. EXPERIMENTAL PROCEDURE A) Growth Technique. The growth apparatus, shown schematically in Fig. 1, and procedure are virtually identical to that described2 for the growth of GaAs1-xPx alloys, with the exception that phosphine is replaced by stibine.* HCl is introduced over the gallium boat to *Purchased from Matheson Co., E. Rutherford,N+J. transport the gallium predominantly via its subchlo-ride to the reaction zone, where it reacts with arsenic and antimony on the substrate surface to form an alloy layer. The fundamental limiting factors to the growth of GaAs1-xSbx alloys from the vapor phase, especially GaSb-rich alloys, are the low melting point of GaSb (712°C) and the low vapor pressure of antimony at this temperature (<l mm). Thus, relatively low antimony pressures must be employed, which, however, imply low growth rates. To provide low antimony pressures, very dilute concentrations of arsine and stibine in a hydrogen carrier gas were used. Typical flow rates (referred to stp) were about 4 cm3 per min of HC1 (0.06 mole pct)+ from 0.1 to 1 cm3 per min of ASH, (0.002 to 0.02 mole pct), and from 1 to 10 cn13 per min of SbH3 (0.02 to 0.2 mole pct), with a total hydrogen carrier gas flow rate of about 6000 cm3 per min. Although no precise data on decomposition. kinetics exist, it is known4 that stibine decomposes extremely rapidly at elevated temperatures. However, the high linear velocities attendent with the high total flow rate (about 2000 cm per sec) delays cracking of the stibine until it reaches the reaction zone and prevents condensation of antimony in the system. To improve the growth rates of the GaSb-rich alloys, growth temperatures just below the alloy solidus are main-

Jan 1, 1970

By J. D. Price, G. V. Woody

MANY producers of by-product coke have spent considerable time and given considerable thought to the use of a substitute for low-volatile coal as an admixture with high-volatile coking coal for charging high-temperature by-product coke ovens. Generally speaking, there are two principal reasons for this, one being occasioned by the lack, in certain localities, of low-volatile coal delivered at a cost sufficiently low to permit its use, and another being the desirability of finding a substitute product with a delivered cost lower than the cost of the low-volatile coal. It was for the first of these reasons that the Colorado Fuel and Iron Corporation was particularly interested in this subject. This paper deals with the experimental work and the results obtained by that company in producing and using low-temperature char. OVERCOMING DEFECTS IN COKE FROM COLORADO COALS Colorado coking coals are all of the high-volatile type and were all laid down during he Cretaceous period, which makes them something like 80 million or so years younger, geologically, than eastern coals. They behave, when coked alone, something like the Pittsburgh-seam coals. They make a very brittle, highly cross-fractured, fingery coke of fair shatter value but quite low in resistance to abrasion. Mixed with a low-volatile coking coal such as Pocahontas or certain Oklahoma coals, they make a coke that is equal to virtually any of the eastern cokes. The inferior quality of Colorado coke has long been recognized, and a considerable amount of time, effort and money has been spent upon investigations of means for improving its physical properties. While it has been found that some improvement in quality of coke can be secured by the adjustment and control of such variables as pulverization, moisture content, oven temperature and bulk density of charge, and through the addition of certain inert materials such as pulverized coke breeze, pitch, high-volatile noncoking or semicoking coal, the benefits so gained have been comparatively small. There are no low or medium-volatile coking coals available within a reasonable freight-cost distance. Therefore a substitute for low-volatile coal was developed through low-temperature carbonization-or, more correctly speaking, through the partial devolatilization-of high-volatile coals. The blending of this lower volatile char with the high-volatile coking coal distinctly improves the quality of coke made from Colorado coal. There is nothing especially new about this idea. In 1908 a Japanese patent was taken out by Kotaro Shimomura, whose claim was: The method of making a nonfingery coke out of bituminous coals, without using natural coals of low-volatile matter; according to which a certain coal is heated at a temperature between about 300°C. and about 600°C. so as to leave about 15 to 25 per cent volatile matter in the coal; this coal is mixed with the

Jan 1, 1944