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By S. A. Levy, J. D. Wood, J. F. Libsch

A study of the preparation and characteristics of a sevies of Fe-C-N alloys has been conducted. X-ray, microhardness, and metallographic data from a series of single-phase alloys produced by controlled nitriding of carburized foils are reported. The existence of a, y', and E carbonitride has been confirmed and it has been found that y' is the hardest of these three phases. These results have been used to interpret the structures observed in nitrided steels. ThIS paper represents the second phase of a three-part study concerning combined nitriding and induction hardening. The first part' reports the engineering properties (depth hardness, fatigue, corrosion, and tempering resistance) obtained when seven different steels were subjected to the combined surface hardening treatment. The present paper concerns the nature of a series of single-phase alloys prepared by controlled nitriding of carburized foils. The objective was to simulate the various layers present in the as-nitrided steels. A third paper will report data concerning induction hardening of the foils and will attempt to set forth a mechanism for the high hardness obtained with the combined treatment. Studies of nitriding generally fall into three categories. The first were performed with bars using conventional nitriding procedures, thus yielding a nitrogen gradient and a series of phase layers near the surface.2-6 Such studies were complicated by the presence of the nitrogen gradient, for it was difficult to correlate microhardness and X-ray data with chemical composition. There were always complications due to penetration of the X-ray beam which yielded data influenced by underlying layers. Similar difficulty was experienced in taking hardness readings on a tapered specimen or in isolating various layers by machining. A second group of investigations was primarily concerned with establishment of regions in the Fe-N7,9,10 or the Fe-C-N phase diagram.8 These were performed with powder specimens which were nitrided in am-monia-hydrogen mixtures to produce a series of single-phase specimens. Unfortunately, the powder specimens were not amenable to either microstruc-ture or microhardness study. The third was essentially a compromise of the first two. Bose and Hawkes," using 0.005-in.-thick iron foils, were able to obtain microhardness, microstruc-ture, composition, and X-ray data on Fe-N alloys of eutectoid composition by equilibration in ammonia-hydrogen mixtures at 1290°F. To obtain a better understanding of the nitriding process and the characteristics of the phases in ni-trided plain carbon steels, the present investigation was undertaken. The investigation was patterned after that of Bose and Hawkes with the exception that nitriding was performed at 930°F (below the eutectoid temperature), as in the case of conventional nitriding. In addition to gaining some understanding of the source of high hardness of nitrided and induction-hardened steels, found in a previous study,' this investigation was concerned with the possibility of controlling the phases present in a nitrided case through the use of ammonia-hydrogen mixtures. Knowledge of the properties of each phase and the conditions necessary for its production could make it possible to avoid undesirable surface layers in nitriding. EXPERIMENTAL PROCEDURE Specimen Preparation. A specimen thickness of 0.005 in. was selected to insure that a uniform nitrogen concentration could be obtained in a reasonable length of time by equilibration in an ammonia-hydro-gen atmosphere. The starting material was a vacuum-cast ingot of pure iron, the major impurities of which were: C, 0.003 pct; 0, 0.014 pct; S, 0.004 pct; N, 0.003 pct.* 'Compositions are quoted as weight percent except as noted. The ingot was heated to 1500°F in a nitrogen atmosphere and forged to a slab 0.25 in. thick. The material was then reduced to 0.005 in. by alternately cold rolling and annealing in a nitrogen atmosphere at 1600°F. This material was divided into five groups of specimens which, after carburizing, yielded the following carbon contents: 0.003, 0.28, 0.36, 0.46, and 0.74 pct C. The carburizing was performed by the Leeds and Northrup Research Laboratories, using a controlled "carburizing potential" which yielded a uniform carbon concentration throughout the cross section.

Jan 1, 1970

By L. W. Holm

This study shows that in the presence of foam, gas and liquid flow separately through porous media representative of reservoir rock. These results were obtained by using tracer techniques to measure the flow of the gas and liquid comprising the foam. Foam does not flow through the porous medium as a body even when the liquid and gas are combined outside the system and injected as foam. Instead, the liquid and gas forming the foam separate as the foam films break and then re-form in the porous system. Liquid moves through the porous medium via the film network of the bubbles and gas moves progressively through the system by breaking and re-forming bubbles throughout the length of the flow path. The flow rates of the gas and liquid are a function of the number and strength of the films in the porous medium. There is no free flow of gas; i.e., no continuous gas phase. On the basis of these results, foam can be expected to improve a water flood or gas drive by decreasing the permeability of the reseruoir rock to a displacing liquid or gas. This improves the mobility ratio and thus the conformance of the flood. INTRODUCTION Foam is formed when gas and a solution of a surface active agent are injected into a porous medium either simultaneously or intermittently. During the past few years, several papers have been published on the subject of foam flow in Dorous media. Foam has been used successfully in the removal of capillary water blocks from producing formations.''2 The use of foam in gas storage reservoirs to reduce gas leaks and to increase storage capacity has been considered in recent years. Foam has also been investigated as an oil displacing agent,3-5 and as an agent to improve the mobility ratio in a waterflood.6-10 However, the mechanism by which the gas and liquid phases comprising the foam flow through a porous medium has nor been described adequately. Normally, when two immiscible phases (gas and liquid) flow concurrently through a porous medium, each phase follows separate paths or channels. At given saturations of the two phases, a certain number of channels are available to each phase, and as saturations change, the number and configuration of the channels available for each phase also change. The effective permeability of each phase is a function of the saturation of that phase only, and the flow of each phase can be described by Darcy's law. When foam is present, the effective permeability of the porous medium to each phase is greatly reduced compaced with permeabilities measured in the absence of foam.6,11-13 Based upon the observed flow of surfactant solutions and gas in capillaries, it has been concluded that the gas and liquid may flow separately or they may flow combined as foam. At least four mechanisms have been postulated to explain how fluids flow with foam present: 1. A large portion of the gas is trapped in the porous medium and a small fraction flows as free gas, following Darcy's law.9 2. The foam structure moves as a body; the rate of gas flow is the same as the rate of liquid flow. 6,13 3. Gas flows as a discontinuous phase by breaking and re-forming films. Liquid flows as a free phase.12 4. A portion of the liquid and gas move as a foam body while excess surfactant solution moves as a free phase.14 It also has been suggested that different flow mechanisms exist for high quality (dry) foams made from dilute surfactant solutions and for foams made from more concentrated solutions. Studies conducted on the flow of foam through capillaries have shown that a plug-type flow occurs and that foam flows as a body.6,15 Fried also has described the flow of foam through porous media as

Jan 1, 1969

By C. Hirayama

THIS investigation was undertaken to determine some of the factors contributing to the embrittle-ment of glass-coated silver wire on heat treatment. The materials used in this investigation were 22 and 23 AWG silver wires obtained from Handy and Harman as "fine quality, soft temper." A wet analysis of one sample showed 99.8 pct Ag. The 23-gage wire was covered with a double layer (2.5 mils thick) of electrical grade fiber glass (aluminum borosilicate glass containing a relatively high concentration of calcium, and a very small amount of

Jan 1, 1960

By W. J. Babyak, J. M. Sheehan, H. W. Paxton

THE- solubility of hydrogen and deuterium in solid niobium up to I-atm pressure has been established bv a number of workers.1-5 X-ray examination at room temperature of specimens reacted in hydrogen at high temperatures from 300° to 1000°C shows the presence of two phases—a bcc phase (a) based on the niobium lattice and with an u0, increasing from 3.30A for Nb to 3.32Afor NbHo.L, and an orthorhombic phase6n = 4.84A, h=4.90A, c =

Jan 1, 1960

By S. W. Ihle, L. J. Warren

A sample of garnet from the scheelite ore body on King Island, Tasmania, Australia, was upgraded and ground to produce an ultrafine portion suitable for micro-electrophoresis. X-ray and chemical analysis identified the garnet as andradite with some admixed grossular. At neutral pH the garnet particles were negatively charged, their zeta potential becoming rapidly more negative with increasing pH. An iso-electric point was found at pH 3.5. The effects on the zeta-potential of various electrolytes, hydrolyzable metal ions, and flotation collectors were also studied.

Jan 1, 1976

By Kenneth E. Gray

The turbulent flow drag coefficients, or friction factors, have been experimentally determined for the cut-tings normally encountered in drilling operations. The gas law and average drag coefficients for characteristically flat particles (limestones and Shales) and for angular to sub-rounded particles (sandstones) were used to extend Newton's equation to a more useful form. The resulting equations are expressions for the slip velocity of a particle as a function of the particle size and shape, the bottom-hole injection Pressure, and the Bottom-hole temperature. The velocities necessary to lift actual rock cuttings as observed in the laboratory were compared with velocities predicted from the derived equations. Results indicate that there is no single correct circulating velocity and that the commonly used 3,000 ft/min linear velocity may he sufficient to lift only very mall particles. The advantage, in terms of horsepower requirements, of cycling high pressure air to obtain lower compression ratios was shown. INTRODUCTION A promising departure from standard rotary hydraulic drilling is air or gas drilling. In many instances the rate of penetration and bit life increases resulting from this method have been very substantial. Further the application of air drilling in areas of lost circulation or water sensitive pay zones has been highly successful. Purpose For the drilling contractor, the practical question remains, "How much air pressure and volume should I have?' lt is necessary to have a reasonable knowledge of the air velocities and pressures required in air drilling operations for the proper design and most advantageous use of surface equipment and for adequate removal of cuttings from the borehole. Eased on experience, most operators agree that at least 3,000 ft/min linear velocity is necessary for satisfactory hole cleaning.' It was the purpose of this investigation to evaluate the drag coefficients, or friction factors, for the cuttings normally encountered in drilling operations, i.e., sandstones, limestones and shales, and to utilize the values obtained to develop an expression for the minimum velocities and pressures (hence the volumes) necessary to lift these cuttings. THEORY Several investigators have done extensive work on the ability of drilling mud to lift bit cuttings. They conclude that the ability of a drilling mud to lift cuttings is dependent on the density difference between the rock being drilled and the drilling mud, the cutting size and shape, the mud flow constants, and the flow state (laminar, transitional or turbulent) of the mud. However, drilling muds are not true fluids but have a variation of viscosity with velocity in laminar flow and a constant apparent viscosity in turbulent flow. A survey of the literature revealed that no experimental work had been done to determine the velocities necessary to lift actual rock cuttings using a compressible fluid such as air or gas. In 1953, Nicolson6 stated that in air drilling fluid mechanics the particles could be assumed spherical in shape and that ; constant drag coefficient of 0.5 could be used due to the highly turbulent flow of the circulating air. By equating the turbulent resistance on the particle to the gravitational force on the particle, he obtained the expression, ^ = 2.67^y ,.......(1) where V, is slip velocity of spherical particle, ft/sec; D is particle diameter, in.; p, is particle density, 1b/ft8; and p, is fluid density, lb/ft3. However, as stated earlier, most operators seem to agree that adequate hole cleaning can be obtained by circulating a sufficient volume of air to give a linear velocity of 3,000 ft/rnin in the annular space. Basic Equation The velocity with which a solid particle freely falls through a fluid will increase until the accelerating force, gravity, is equal to the resisting forces, buoyancy due to the fluid displaced by the particle and friction due to the relative motion of the particle through the fluid. When the accelerating and resisting forces become equal,

By W. D. Lacabanne

DRILLING fluids as an aid in drilling holes into the earth have been in use successfully for more than a half a century. Originally used in a primitive fashion in water well drilling before the turn of the century, drilling fluids came into their own in 1901 when they were incorporated as an indispensable part of the newly invented rotary oil drilling method. Since drilling fluids have been the basic factor in successful modern oil well drilling, at- tested by the dramatic growth of the U. S. petroleum industry, their study and development have naturally taken place in the oil industry. An abundance of engineering and scientific literature has appeared on the subject of drilling fluids. Application to Exploration Drilling The drilling fluid system is understandably called the heart of the rotary oil drilling rig. Any other type of rotary rig, such as the diamond drill, should benefit by the incorporation of mud fluids in the drilling scheme.

Jan 12, 1954

By B. K. Larkin, H. R. Bailey

A model Of heat flow in an underground combustion process is studied. This model includes convection effects and thus is more general than previous studies which considered conduction as the only mechanistn for heat transfer. Both linear (tube run) and radial (field application) geometries are considered. The effects of ignition heaters, vertical losses and finite source width are considered for the linear case. The results are in the form of equations and are presented in graphical form for a number of cases. Convection effects increase frontal temperatures about 25 per cent over those computed for conductive transfer for typical field operating conditions. This increase in temperature is a result of heat being transported toward the front by the injection gas. Even greater temperature increases are realized as the per cent oxygen in the injection gas decreases. It is well known that compression costs are of considerable importance in estimating the economic feasibility of underground combustion. By assuming an ignition temperature for the combustion fuel, predictions of limiting conditions on fuel density and injection rate necessary to sustain the combustion zone are made. For typical field conditions, at least 0.75 lb/cu ft of fuel are needed with air as the injection gas. If the injection gas is 10 per cent oxygen and 90 per cent nitrogen, this figure is 0.69 lb/cu ft. INTRODUCTION The possibility of increasing oil recovery by underground combustion has been considered for many years. Recent field tests indicate that the underground combustion process is technically feasible. The economic feasibility depends to a large extent on the amount of air which must be injected to sustain combustion. Prediction of the success of employing underground combustion in a particular reservoir must be based on existing field tests, laboratory tube runs"' and solutions of mathematical or analog models. Vogel and Krueger5 devised an electrical analog of the heat transfer problem in an underground combus-ion process. They considered the problem of heat conduction from a cylindrical source with increasing radius assuming no vertical losses. Bailey and Larkin and Ramey solved the corresponding problem including vertical losses by considering a mathematical model of the conduction process. Ref. 9, 10 and 11 also present information related to the subject study. The present paper generalizes these results to include both conduction and convection mechanisms for heat flow. A model of the conduction-convection process is described. The partial differential equations governing this model are written and solved for a number of cases of interest. The formulas are evaluated and the results are presented graphically. A CONDUCTION-CONVECTION MODEL Description of the Model A number of models are employed in this paper, each of which approximate a particular physical situation depending on the geometry, i.e., linear or radial flow, the type of vertical heat losses, the nature of the source, etc. The geometry for both the linear and radial case is shown in Fig. 1. A particular linear model is described in this section, and variations from this model are described in later sections of the paper. Consider a homogeneous, semi-infinite porous prism with lateral sides insulated as shown in Fig. 1. The left end, x = 0, is heated for a time t, with a plane heater supplying a constant heat flux and during this time; gas (nitrogen) is passed through the pores of the prism at a constant mass flux. At time t, the heater is turned off and air is injected in place of the nitrogen. This causes combustion to take place, and a uniform source of width 1 is formed which moves at a constant velocity v, to the right. The frontal velocity v, is related to the gas velocity v,, through stoichiometric considerations

By Ramachandra Rao

THE occurrence of copper ores at Garimenapenta, 14 59 min 30 sec N Lat., 79 33 min 10 sec E Long., in Nellore district, Madras State, India, has been examined and investigated on numerous occasions during the past two centuries.' No tangible orebody was ever located as a result of all the ex- tensive trenching and shafting done in the area by various agencies. However, during 1933 Messrs. Piepmeyer & Co., a German firm engaged by one of the leaseholders of the area, carried out an electrical survey using inductive methods.' On the basis of certain strong indications found in their survey, they recommended that the prospect be proved by drilling or shafting. But for want of financial backing no further work was carried out. When the Madras government more recently proposed investigation, Dr. Krishnan, then Supt. Geologist of the Madras Circle, urged that before further costly ventures were carried out a test geo-

Jan 1, 1954

By J. Chipman, J. C. Fulton

Reduction of Si from slag to carbon-saturated iron is a very slow reaction. The rate is nearly independent of stirring but is accelerated markedly by increased temperature. In a slag containing 45 pct SiO2, 38 pct CaO, 17 pct Al2O3, the energy of activation is approximately 130 kcal. AT temperatures of 1450" to 1600°C occurring in the hearth of the iron blast furnace, chemical reactions are normally expected to proceed with great rapidity. Many of the reactions of iron making are indeed quite rapid and attain a condition corresponding roughly to a state of equilibrium before metal and slag are tapped from the furnace. The one conspicuous exception is the reaction by which carbon in the coke or metal reacts with silica in the slag to deliver silicon to the metal. From the practical viewpoint the slowness of this reaction is indeed fortunate, for if it were fast enough to reach equilibrium during the time of contact, it would be difficult to produce pig iron of the desired low silicon content. The one other reaction which under certain circumstances can also be very slow is the transfer of sulfur from blast-furnace metal to slag. In their laboratory exeriments on this reaction, Hatch and Chipman found that at least 5 hr were required for the attainment of equilibrium in a small crucible and that the reaction was not accelerated by increasing the rate of stirring. Subsequently it was shown2 that the presence of a reducible oxide MnO greatly inhibited sulfur removal, and finally that SiO2 itself3 under some conditions has sufficient oxidizing Dower to interfere with sulfur transfer. The kinetics of sulfur removal are now rather well understood,4 and it has been shown3,5 that when the silicon content of the metal is high enough to prevent reduction of SiO,, the desulfurizing process is rapid. Thus the observations of slow removal of sulfur are associated with the coincident slow reduction of SiO2, a process which transfers both silicon and oxygen to the metal phase. It is, of course, the oxygen which interferes with sulfur removal. An explanation of the slowness of the silica reduction reaction has not been obtained. The sulfur transfer process has been shown by the authors5 to be at least partially transport-controlled in the absence of interference by silica. Under the experimental conditions. 99 pct of the total transfer at 1600" was accomplished within an hour. Under similar conditions the reduction of silica may not proceed half-way to equilibrium6 in 8 hr. It is scarcely imaginable that silica reduction could be transport-controlled when the slag contains 44 pct SiO2 and the metal about 1.4 pct C. The experiments reported here show definitely that it is controlled by a slow step or steps in the chemical reaction. One might expect to find such a slow step in the breaking of SiO bonds or in the slow removal of oxygen by carbon at the slag-metal or metal-crucible interface or by bubble formation. EXPERIMENTAL PROCEDURE The experimental procedure used in this investigation was similar to that used in the study of the kinetics of desulfurization.5 A sketch of the graphite crucible and stirrer used in the current work is shown in Fig. 1. The quantity of metal and slag used was adjusted so that the slag-metal interface was located between the top and bottom blades on the stirrer; the top of the slag layer was above the top blade. The stirrer shaft was hollow down to the metal level and served as thermocouple well or optical pyrometer target. Stirring speeds of 0 to 500 rpm were used. A carbon monoxide atmosphere was maintained in the furnace by flushing the gas over the slag surface, except in run No. 220 when it was bubbled

Jan 1, 1960

By Charles Stein

The effects of several different prior treatments an the creep behavior of 99.9995 pct aluminum at 260°C and 1000 psi canstant stress are compared with annealed specimens. Quenching from 538oC, irradiation with 2 mev electrons, and tension-compression room temperature fatigue damage were used to change the substructure of the specimens prior to their creep testing. The quenched and the irradiated specimens showed a larger primary and transient stage contribution to the creep curve than those specimens which were only annealed prim to creep testing. The specimen receiving prior fatigue damage at room temperature showed no first stage or transient creep when tested under identical conditions as the above specimens and had an average creep rate seven orders of magnitude lower than that of either the annealed, the quenched or the irradiated creep specimens. In a previous electron transmission microscopy investigationl of the substructure developed during the creep of pure aluminum at 0.57 Tm, it was noted that a large concentration of vacancy loops and dislocation loops were present in and near the subboundaries while the interior of the subgrains contained few of these defects and had a low dislocation density, see Fig. 1. Yim and Grant2 and Hazlett3 have shown that the presence in nickel of a substructure developed by prior cold work effectively reduces the primary and transient contributions to the creep curve. Hultgren,4 McLean,5 Gervais, Norton, and Grant,6 Chang and Grant,7 and others have shown the same effect with the higher stacking fault energy material, aluminum. However, the specific defect responsible for the change in the creep behavior developed by the prior cold work was not established. Specifically, what effectively interfered with dislocation motion in these materials at elevated temperatures? Was it jogs on dislocations produced by their interaction with other dislocations or with vacancy or dipole loops, see Fig. 1, or did the subgrain walls determine the mean free path for glissile dislocations? This would be a realistic possibility only if subgrain boundaries are effective barriers to dislocation motion. The ability of a subgrain boundary to act effectively against glissile dislocations depends on the number and the arrangement of dislocations in the subboundary,8 which in turn is a function of the creep strain.' This paper compares the creep rate of specimens possessing a large vacancy concentration to that of annealed specimens and with specimens having a stable subboundary wall containing Lomer locks produced by prior fatigue damage. EXPERIMENTAL PROCEDURE Vacancy Loops. Aluminum creep specimens, 99.9995 pct pure, were machined from zone refined rod to a 2-in. gage length and a cross-sectional area of 0.025 in. These specimens were annealed at 538oC, 1000°F, for 10 min and quenched into ice water. They were then reheated to the creep test temperature of 260°C, 500°F, and held at this temperature for 18 min to al-low for vacancy condensation and loop formation. The specimens were subsequently creep tested at 1000 psi constant stress at 260°C. The temperature along the gage length was monitored by three Pt-Pt, 13 pct Rh thermocouples, two embedded in the upper and lower shoulders of the specimen and one attached to the mid-point of the gage length- The temperature gradient was held to ± l°C or less throughout the Creep test. Elongations were measured by two LVDT's 'connected in an averaging 'On-figuration, with quartz extension arms placed against the specimen at the extremes of the 2-in. gage length. i K 3J?--' * *H - >^> - ' ^L r 77 . *y J OJL, J Fig. 1—Transmission electron micrograph of pure aluminum strained 8.2 pct at 260°C and 1000 psi constant stress. Note the presence of numerous loops near the light dislocation tangle

Jan 1, 1970

By B. Haimson, C. Fairhurst

A criterion is Proposed for the initiation of vertical hydraulic fracturing taking into consideration the three stress fields around the wellbore. These fields arise from (1) nonhydrostatic regional stresses in earth, (2) the difference between the fluid pressure in the wellbore and the formation fluid pressure and (3) the radial fluid flow through porous rock from the wellbore into the formation due to this pressure difference. The wellbore fluid pressure required to initiate a fracture (assuming elastic rock and a smooth wellbore wall) is a function of the porous elastic constants of the rock, the two unequal horizontal principal regional stresses, the tensile strength of the rock and the formation fluid pressure. A constant injection rate will extend the fracture to a point where equilibrium is reached and then, to keep the fracture open, the pressure required is a function of the porous elastic constants of the rock, the component of the regional stress normal to the plane of the fracture, the formation fluid pressure and the dimensions of the crack. The same expression may also be used to estimate the vertical fracture width, provided all other variables are known. The derived equations for the initiation and extension pressures in vertical fracturing may be employed to solve for the two horizontal, regional, principal stresses in the rock. INTRODUCTION Well stimulation by hydraulic fracturing is a common practice today in the petroleum industry. However, this stimulation process is not a guaranteed success; hence, the deep interest shown by the petroleum companies in better understanding the mechanism that brings about rock fracturing, fracture extension and productivity increase. Geologists and mining people became interested in hydraulic fracturing from a different point of view: the method may possibly be employed to determine the magnitude and direction of the principal stresses of great depth. Numerous articles in past years have dealt with the theory of hydraulic fracturing, but they all seem to underestimate the effect of stresses around the wellbore due to penetration of some of the injected fluid into the porous formation.1-4 Excellent papers on stresses in porous materials due to fluid flow have been published5,6 but no real attempt has been made to show the effect of these stresses in the form of a more complete criterion for vertical hydraulic fracturing initiation and extension. This paper is such an attempt. ASSUMPTIONS It is assumed that rock in the oil-bearing formation is elastic, porous, isotropic and homogeneous. The formation is under a nonhydrostatic state of regional stress with one of the principal regional stresses acting parallel to the vertical axis of the wellbore. This assumption is justified in areas where rock formations do not dip at steep angles and where the surface of the earth is relatively flat. This vertical principal regional stress equals the pressure of the overlying rock, i.e., S33 = —pD, where S33 is the total vertical principal stress (positive for tension), p is average density of the overlying material and D is the depth of the point where S33 is calculated. The wellbore wall in the formation is considered to be smooth and circular in cross-section. The fluid flow through the porous elastic rock obeys Darcy's law. The whole medium is looked upon as an infinitely long cylinder with its axis along the axis of the wellbore. The radius of the cylinder is also very large. Over the range of depth at which the oil-bearing formation occurs, it will be assumed that any horizontal cross-section of the cylinder is subjected to the same stress distribution, and likewise that it will deform in the same manner. STATE OF STRESS PRIOR TO DRILLING OF WELLBORE At a depth D from the earth surface within the oil-bearing strata, it is assumed that the following are 1References given at end of paper.

By AIME AIME

MORE than thirty members of the Coal Division attended the Coal Land Valuations Round Table on Monday morning. Chairman Dilworth stated that the Committee had been appointed to take up the question and, after reading the list of members of the Committee, pointed out that the object of the meeting was to formulate a plan of action rather than to discuss any phases of valuation, per se. To this end he presented a tentative outline of points to be considered in the future by the Committee. After a lively discussion on the desirability of inclusion of some questions in the agenda of the Committee, the following outline was adopted :

Jan 1, 1931

By B. Hyatt, E. Klokholm

The reesistivity of Cu-Pd alloys of 9.6 to 29 pct Pd alloys was measured after plastic deformzation in tension. For all compositions a continzting decrease in resistivity with increasing plastic strain was observed. By comparison with the results of Damask on a brass ad Cu3Au, it was deduced that these anonzalous decreases in resistivity are due to the decrease in short-vunge order caused by cold work. An anomalous decrease in the resistivity of cold-worked CU-Pd alloys was first reported by Jaumot and Sawatzky.' They observed decreases in the electrical resistivity when disordered Cu-Pd alloys drawing at room temperature. Recently, a similar anomaly was reported by Aarts and Houston-Mac-Mi1lan2 in Ag-Pd alloys containing 10 to 45 pct Pd. The plastic deformation in this case was produced by tensile strain at liquid-nitrogen temperatures. For AE-Pd alloys the relative resistivity change becomes positive for tensile strains of about 20 pct.

Jan 1, 1960

By E. Martinez, M. L. Hollander

Sulfurization of copper oxides was investigated using differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). When mixtures of cuprous oxide and sulfur were heated, the surface of the cuprous oxide was converted to cupric sulfide at the melting point of sulfur (119°C); additional sulfuriza-tion took place when the sulfur vaporized above 200°C. Cupric oxide also reacted with sulfur to form cupric sulfide but the starting temperature was approximtely 225°C. When the cupric oxide and sulfur were physically separated, sulfurization still occurred indicating a reaction with the vapor phase of sulfur. Sulfurization was obtained in runs with cuprite, chrysocolla and basic copper carbonate. Further decomposition of cupric to cuprous sulfide was noted at somewhat higher temperatures. The DTA-TGA data made it possible to set up postulated reactions in each system. These techniques were found to be well suited for studies of this type. Because of the difficulty encountered in flotation of many metallic oxide minerals, efforts have been made to find suitable reagent combinations to sulfi-dize these minerals in the flotation circuit. Recently Bautista and Sollenberger,1 using a different approach, showed that the surfaces of many oxide minerals can be converted to sulfides by heating them with sulfur to temperatures between 150° and 225°C. This technique was effective even with chrysocolla, a mineral which is very difficult to sulfidize. The primary objective of the present study was to obtain information on the reactions between the oxide minerals and suIfur. A better understanding of the mechanisms involved might prove useful in pointing the way to improvements in the process. A secondary objective was to demonstrate the value of thermo-analysis in investigations of this type. Bollin and Kerr2 have reported the use of a modification of differential thermal analysis to study the thermal reactions which occur on heating elemental constituents in a closed system to synthesize copper sulfides and iron sulfides. Differential thermal analysis (DTA) was used to detect enthalpic changes as mixtures of minerals and sulfur were heated. The DTA indicated the temperatures at which reactions started and whether they were exothermic or endothermic. Weight change data were obtained by thermal gravimetric analysis (TGA). These data could often be used to support postulated reactions and to eliminate consideration of other possible reactions. EQUlPMENT Differential thermal analysis (DTA) involves measuring the temperature difference between the sample being tested and a thermally inert reference, generally aluminum oxide, as both are heated at a uniform rate. Series connected thermocouples in the sample and reference are used to detect the temperature differences that occur as the sample undergoes enthalpic changes.3 Crystalline transitions, fusions, vaporizations, dehydrations, decompositions and many solid state reactions can be detected. A DTA unit manufactured by the Robert L. Stone Co., Austin, Tex., was used in this investigation with a temperature rate increase of 10°C per min. The samples and reference were placed in Inconel cups with wells in the bottom into which the differential thermocouples fit, and run in a nitrogen atmosphere. Thermal gravimetric analysis (TGA) measures the changes in weight that a sample undergoes as it is heated. A Chevenard thermobalance converted electronically for graphic recording was used with a heating rate of 5°C per minute. An X-Y recorder plotted temperature on the X axis and weight changes on the Y axis. A flow of 250 ml per min of nitrogen was streamed through the furnace. Samples were placed in a porcelain crucible open at the top, unless otherwise noted. EXPERIMENTAL RESULTS Sulfur: Two sulfur samples from different sources were tested. The DTA of a high purity sulfur and a reagent grade sublimed sulfur are shown in Fig. 1. Nearly all the tests were run with the sublimed sulfur due to the difficulty in grinding and high electrostatic charge encountered with the high purity sample. Sulfur undergoes three endothermal reactions below 200°C. The first is a solid-solid crystalline transi-

Jan 1, 1964

Jan 1, 1911

By Oren C. Baptist, Eliot J. White

Samples of four reservoir sands having different degrees of water sensitivity were subjected to several laboratory tests to determine differences in capillary behavior attributable to clay-mineral effects. The degree of water sensitivity was estimated by the difference between gas and water permeability. Unsaturated pore volumes determined with mercury injection were comparable to irreducible water saturations determined with the semipermeable bar-rier method only for the non-sensitive sands that contained small amounts of non-swelling clay minerals. Irreducible saturations were independent of salinity of the water, which suggests that most residual water is adsorbed 0.7 a film over solid surfaces and that internal retention by clay minerals is relatively insignificant. The water-sensitive sands imbibed water to higher saturations than did non-sensitive sands, and this result is believed to be a combination of the effects of clay minerals and preferential wettability; however, the relative importance of each of these effects is riot determinable. Thus it is concluded that the semipermeable barrier method is the best of the laborafory methods used for estimating formntion water .saturations in the sands studied. INTRODUCTION This investigation is a continuation of studies of the role of clay minerals in petroleum production in the Rocky Mountain area. Previous work has shown large differences in gas and water permeability in numerous reservoir sands; these water-sensitivity effects observed in the laboratory have been correlated with well behavior in the field, and the degree of water sensitivity imparted to reservoirs by the various clay minerals has been determined.'.' The effect of interstitial clay minerals on formation water3 saturations is not so well known. It has been reported that formation water saturations probably are higher in clayey than clean sands,' but this effect has not been evaluated in the laboratory, and the relative effect of the various types of clay minerals on formation water saturation has not been determined. The clay-mineral groups of most importance to this study and to petroleum production in general are kaolinite, illite, and montmorillonite. The minute layers of montmorillonite are loosely bound to one another so that water enters between them, causing great expansion of the particles. Kaolinite and illite do not exhibit interlayer hydration, but they do immobilize considerable amounts of water owing to their large surface areas, which are of the order of 15 to 97 m2/gm of clay.5 The four Wyoming sands used in this study were selected to represent a wide range of water sensitivities. These sands, with the number of wells and fields from which the samples were obtained, are: Second Frontier, five wells in two fields; Newcastle, six wells in one field; Tensleep, two wells in two fields; and Lower Muddy, five wells in one field. EXPERIMENTAL METHODS AND PROCEDURES Water-displacement data were obtained by the semipermeable barrier method," using both fresh water and brines having either 16,500 ppm sodium chloride or calcium chloride. A displacement pressure of 35 psi was found to be sufficient to obtain the practical irreducible water or brine saturation (IWS, IBS) in most samples. Mercury-injection data were ob-tained with equipment and pro-cedures similar to those described by Purcell.7 Exceedingly high pressures are required to attain complete mercury saturation by this method; however, since saturations in most samples change very little with large pressure increases above 1,000 psia, the maximum pressure used was 1,400 psia. To facilitate comparison of mercury-injection and water-displacement results, it is convenient to express mercury-injection data in terms of unsaturated pore volume. The abbreviation, (100 - SHg)min, is used to denote the pore volume unsaturated by mercury at 1,400 psia injection pressure. Gas permeabilities, ki, were deter-mined by the method proposed by Klinkenberg.8 Methods of determining types and amounts of clay minerals by X-ray diffraction analyses, as well as methods of determining water permeability, have been described previously.' The imbibition characteristics of

Jan 1, 1958

By J. Pinto, F. Galasso

THE current emphasis in preparing boron fibers by reduction of gaseous boron compounds on a resistively heated metal wire substrate has renewed interest in the borides of those metals which have relatively high melting points and are available as fine wires. A knowledge of the structures and properties of the borides, which are formed when boron diffuses into the metal core during boron deposition, can be of assistance in the understanding of the boron fiber formation process and the fiber properties. Many of these borides are well-known and their properties have been measured. However, when an unidentified boride is found in the core, it may be difficult to establish its composition because of the small amount of material available, the preferred orientation effects on the reflections in its X-ray pattern, and the possible overlap of X-ray reflections if several borides are present in the core. For example. the proper indexing of the X-ray pattern of WB4, which was formed in the tungsten substrate core during boron fiber formation, was accomplished only after small single crystals of this boride were grown and X-ray precession investigations were conducted.' This note presents the results of a study of the phases formed in the core when tungsten, tantalum, and molybdenum metal wires were used as substrates in the boron fiber preparation process with particular emphasis on the identification and characterization of a higher boride of molybdenum analogous to WB,. Boron was deposited on resistively heated stationary 0.0012-in.-diam tantalum, tungsten, and molybdenum wires at 1050°C for various times up to 60 sec using boron trichloride and hydrogen as the reactant gases. After 60 sec of boron deposition the fibers were approximately 0.006 in. in diam. Examination of photomicrographs of fiber cross sections showed that the boron had diffused nearly to the center of the tungsten and molybdenum cores in 15 and 30 sec, respectively, and only halfway to the center of the tantalum core in 60 sec. X-ray diffraction photographs of the fibers indicated that it was also after 15 and 30 sec deposition times that the tungsten and molybdenum metal reflections, respectively, had disappeared from the X-ray patterns of the fibers. The patterns of the boron fibers produced using tantalum wire as a substrate showed that amorphous boron, TaB2, and tantalum metal were present after a few seconds deposition time and remained even after deposition times of 60 sec. Until a deposition time of 15 sec was reached, the tungsten substrate fibers contained amorphous boron,273 6WB, W2B5, and WB4 as well as tungsten metal, while the molybdenum substrate fibers contained amorphous boron, MoBa, Mo2B5, and molybdenum metal for deposition times up to 30 sec. Just before the molybdenum metal pattern disappeared, a pattern similar to that of WB, appeared, suggesting that a phase, MOB,, isomorphous with WB,, was present in the fiber. This same pattern was obtained from the product formed by heating a mixture of molybdenum metal and excess boron powder in a boron nitride crucible at 1960°C in an argon atmosphere. As was the case with the WBn pattern, this pattern could best be indexed on the basis of a hexagonal unit cell rather than the tetragonal unit cell Chrktien and Helgorsky reported for ~0~4,~ see Table I. The unit cell parameters for MoB4 were calculated to be a, = 5.214A, co = 6.358A. Assuming the space group P63/mmc and positions5 2M01 in 2b and 2MoII in 2c found for tungsten in WB~,' a logical structure for MOB, was determined using geometrical considerations to place the boron

Jan 1, 1969

By J. Chipman, H. Towers, M. Paris

A simple radioactive tracer technique is used to measure the diffusion coefficient of calcium ion in molten slags. In a slag of 40 pct Ca0-40 pct Si0,-20 pct Al203, Dc " at 1450°C is 1.3x10-6 cm' sec-'. THE application of the principles of thermodynamics to steel and iron making problems has proved so fruitful that the kinetic approach has tended to be neglected. It seems probable that in some reactions the rate-determining step is the dif-fusivity of the reactants or of the products. But knowledge of the diffusion coefficients of the constituents of liquid slag and metal is singularly lacking. The present work was undertaken as a first step toward supplying such data for slags. Furthermore, any additional information on the physical properties of liquid slags might be expected to help in elucidating their structure. It is essentially a preliminary investigation, the course of which was determined more by the necessity of establishing a method than by the immediate intrinsic interest of the results. For example, the selection of calcium ion to be studied was dictated by the suitability of the isotope Ca45 in that it is a simple emitter with a long half-life. Of the other ions commonly encountered in slags, the isotopes of iron and manganese have relatively complex radiations as well as the normal disadvantage of requiring control of the oxygen potential of the atmosphere; Mg27 and Al29 have half-lives measured only in minutes; Si3' has a simple decay process but its half-life of 2.8 hr is too short for preliminary studies; the only useful oxygen isotope is the stable O18; and there remain only sulphur and phosphorus both of which have suitable isotopes but were rejected as being of less fundamental interest than calcium. Similarly a lime-alumina- silica slag was used in preference to calcium silicate primarily because of its low melting point and its capacity to form a glass on fairly rapid cooling. Literature Review Very few studies of diffusion in liquid silicate systems have been reported. In order to determine the origin of diopside inclusions in felspathic rocks, Bowen1 investigated the diffusion between diopside and various mixtures of albite and anorthite. Platinum crucibles were used with diopside, the heavier of the two liquids, forming the lower half of the cell and diffusion taking place against gravity. Change in concentration along the diffusion path was found by measuring the refractive index of the quenched glass. Nearly thirty years later McCallum and Barrett2 used essentially the same method to determine the diffusion coefficient of lime in lime-alumina-silica slags. In this case the interest was to find the rate-determining step in the process of slag attack on refractory materials. In an investigation of the kinetics of the sulphur reaction, Derge, Philbrook, and Goldman8 determined the diffusion coefficient of sulphur in a typical blast furnace slag by the simple procedure of melting a slag containing 2 pct S over an identical slag sulphur-free. They make no claim to a high degree of accuracy but suggest that D, is of the order of 10-6 cm2 sec-l. Other high temperature liquid diffusion studies have been concerned with metals. Holbrook, Furnas, and Joseph4 determined the diffusion coefficients of silicon, phosphorus, sulphur, manganese, and carbon in liquid iron by immersing a small carbon crucible containing pure iron-carbon alloy in a large vessel containing iron with a high concentration of the particular element. Their results were confirmed by Paschke and Hauttmann5 using a similar method. Diffusion coefficients in silicates in the glassy state have been studied by Johnson, Bristow, and Blau6 Both Na24 and Ca45 were used as tracers but only the

Jan 1, 1954

[Trans. No. Place Date Vol. Page 1. Wilkes-Barre, Pa May, '71.. 1 3 2. Bethlehem, I's Aug., '71.. 110 3. Troy, N. Y Nov., '71.. 113 4. Philadelphia, PaFeb., '72.. 117 5. New York, N. YMay, '72120 6. Pittsburgh, Pa Oct., '72.. 125 7. Boston, MassFeb., '73.. 128 8. Philadelphia, Pa.*May, '73.. 23 9. Easton, PaOct., '73.. 27 10. New York, N. Y Feb., '74211] [ ]

Jan 1, 1925