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By J. E. Gruzleski, O. Knacke, M. J. Meixner

The evolution of CO from small specimens of solidifying steel was investigated using a thermobalance technique. Gas evolution begins in the temperature range between 1400" to .1450°C. This behavior is independent of the initial carbon content and the cooling rate. At a constant temperature above 1220°C, the rate of gas evolution is temperature independent. Out-gassing of the specimen is thought to proceed through small channels formed by the coalescence of bubbles between dendrites. LIQUID metals have a higher solubility for gas than the solid. During freezing, these gases form bubbles which may either escape or remain trapped in the solid. Recent work1 on the evolution of oxygen from solidifying silver showed that the gas is not liberated until a large fraction of the melt has solidified, and that the gas is evolved in an almost explosive manner. Because of the commercial importance of CO evolution in solidifying steel, a similar investigation was undertaken to study the mechanism of gas liberation in steel. EXPERIMENTAL The thermogravimetric method of Knacke and eixner1 to follow gas evolution by weight changes was employed. Weight differences of 0.1 mg could be reproducibly measured on specimens weighing 2.5 g. These specimens were taken from alloys with varying carbon contents from <0.01 to 0.11 wt pct and <0.01 wt pct of each of silicon, manganese, and aluminum. Specimens contained in 8 mm ID magnesium alumi-nate crucibles were heated to 1550°C under 1 atm of very pure (99.995 pct) CO with a tungsten resistance furnace. The specimen temperature was measured with a Pt-Pt/Rh thermocouple located directly beside the crucible. It is felt that the temperature thus measured was within 5" to 10°C of the specimen temperature since on fusion the weight of the specimen increased due to uptake of CO, and this weight increase was always observed to begin within the temperature range of 1530" to 1540°C. Even after 3 hr there was a small weight increase with time indicating that the molten specimen was not completely saturated with CO. Therefore, complete saturation was not attempted, and all specimens were simply held for 3 hr at 1550°C before cooling. Two types of cooling experiments were performed. One consisted of continuous cooling at linear rates from 5°C to 20°C per min down to 1020°C. The second type of experiment involved continuous cooling at 10°C per min to a predetermined temperature, and then holding the specimen at this temperature for a certain time. During all of these experiments, the sample weight was recorded as a function of time and temperature. OBSERVATIONS Continuous Cooling Experiments. No gas evolution was detected above 1450°C. The initial weight decrease always occurred between 1400" and 1450°C with the average at 1430°C. With further cooling, gas evolution continued to about 1150°C. Between this temperature and 1020°C no further outgassing was observed. This behavior did not seem to depend on the initial carbon content nor on the cooling rate in the range investigated. Typical patterns of gas evolution are shown in Figs. 1 and 2 for different initial carbon levels and cooling rates. The total amount of gas liberated during solidification varied with the rate of cooling. The total weight change on continuous cooling at a rate of 10°C per min

Jan 1, 1970

A plan which has just been approved by President Wilson, by, the Secretary of the Navy, and the Naval Consulting Board, provides for the active cooperation of the Associated Advertising Clubs of the World with the 30,000 engineers who will soon undertake the task of making a card index survey of American industry, so that it may be prepared for national defense, if need comes. Herbert S. Houston, President of the Associated Clubs of the World comments on the plan. "Through the great power of advertising we expect-to arouse manufacturers, workingmen, businessmen, in fact the whole country, to the vital need of making industry the basic line of defense so that, if necessity arises, it can supply munitions quickly and abundantly. "This is not a war measure, but a peace measure. The militarist will support it and so will the pacifist, as well as the great body of Americans in between. So the slogan `national defense and international peace, has been adopted believing that the two causes will be best served by linking them together. "While the primary thing, of course, is service to the country, it is manifest that this work of the engineers will be of the greatest service to industry in times of peace. If industry is mobilized for defense, it will be placed on a basis of efficiency to meet the keen competition that will surely follow the present war." Howard E. Coffin, one of the leaders of the American automobile industry, in outlining the far-reaching plans of his committee, the Committee of Industrial Preparedness of the Naval Consulting Board, said: "At the outset I wish to emphasize the absolutely non-partisan nature of this work. I am not even familiar with the political affiliations of the great majority of the members of the Board or of my committee. In setting out to, mobilize the industrial resources of the United States, we are concerned only with the benefit to the nation, and to that end we have called into being an organization made up of the best technical and business brains of the country, and that organization will work along business lines with strictly business methods. I think it reasonable to say that this is a movement perhaps unique in the history of national governments, and one geared up to the highest standards of twentieth century efficiency. "It is vitally necessary that American industry be made aware of the part it must play in the national defense. Our whole conception of warfare has been changed almost overnight. Our military heads at Washington are largely, of course, graduates of the very best technical schools, have been taught the profession of fighting, and are masters of that profession. As members of the Naval Consulting Board, we are unable to tell these men how to do their work. But while these departmental heads have lived with military problems all their adult years, we on the other hand have slept and eaten and lived with the industrial problems of the country. The two questions are wholly distinct, and the masters of one cannot possibly be the masters of the other. We are confronted then with the necessity of interlocking these two vast elements of our national life into a great working organization for the national defense. It is that which we are about to do.

Jan 5, 1916

By L. C. Armstrong

Twice in the past two years and in two widely separated localities—ane near Williamsville, Mo., and the other in the Allard Lake district of Quebec— the Contract Drilling Division of the Longyear Company has experienced perplexing difficulties in drilling granitoid igneous rocks. The rocks in both places are characterized by appreciable amounts of feldspar intimately inter-grown with quartz particles of microscopic dimensions. The disappointingly slow rate of advance and the exceptionally high bortz loss, obtaining during the life of these two projects, are ascribed largely to the resistance to abrasion of these two minerals when arranged in this intergrown pattern. Whether all intergrowth-bearing igneous rocks would offer extraordinary resistance to bit progress cannot be stated with assurance on the strength of these experiences alone. More data on diamond drilling this sort of material in a number of localities are needed before any generalizations can be made safely. It should be pointed out that the lack of time and funds made it impossible for the writer, or other persons interested in correlating the details of bit histories with the kinds of rocks drilled, to be present during the performance of the contracts. However, the records kept in the normal course of drilling are deemed complete enough to be reportworthy. This information is presented here together with the findings made in studies of the rocks involved, with the thought that it may attract the comments of others who may have encountered similar refractory drilling conditions. A pooling of knowledge on the problem would be of material aid in devising more efficient cutting tools and procedures for penetrating this kind of rock. Drilling Blastholes in the Williamsville Granite Due to the unsatisfactory perform- ance of pneumatic percussion drills in boring blastholes on a construction contract near Williamsville, Mo., tests were made with a diamond drill. The poor progress achieved and the excessive loss of diamonds, however, soon led to the abandonment of these trials. The diamonds, in all of the bits tried, lost their cutting edges and acquired a polish after being in service for distances ranging from a few inches to a few feet. Coring bits containing surface-set, whole-stone bortz in a tungsten powder matrix were employed. The cost assignable to bortz wear averaged $7.17 per foot. This item of expense is several times the amount normally expended in diamond drilling in firm, unfractured, granitic rocks. Diamond-impregnated, tungsten carbide bits also were used without success. The diamond wear was at the rate of $0.98 per foot, but the diamond chips became too polished for further duty in less than a foot of drilling. The Williamsville granite is pink and medium-grained. In the hand specimen, it has a fresh, sound appearance; it is seemingly composed almost entirely of interlocking grains of feldspar and quartz and has no discernible features suggesting a greater durability than is usually found in rocks with this composition and texture. Microscopic examination, however, reveals a predominance of feldspar grains with more or less regularly distributed and sharply angular masses of quartz (see Fig 1). The pattern assumed by the two minerals in this mode of occurrence is referred to as a "graphic intergrowth," as it bears some resemblance to the cuneiform characters of ancient Persian writing. The other principal constituents are quartz-free feldspars (microcline and orthoclase) and quartz. All of these constituents are in nearly equidimensional grains, ranging up to about 3 mm in length. There are also

Jan 1, 1950

By W. Philippoff, Donald E. Cadwell, S. R. B. Cooke

THE importance of contact angles in flotation has long been recognized, but little has been done to get quantitative relationships between the surface coverage of the mineral by the reagent, the length of the hydrocarbon chain, and the contact angle. It is well known that for a complete monolayer on the surface of a mineral the contact angle 8 is determined only by the reagent1 and principally by the chain length of the hydrocarbon radical. Although for flotation the monolayer usually is regarded as being complete, early experiments of Wark and Cox&apos; showed that at very small concentrations of potassium ethyl xanthate the contact angle on galena changed in a continuous way from 0&apos; to the equilibrium value of 60". Further, Gaudin and Vincenta showed a similar continuity using heptylic acid and sphalerite. This shows that with probably incomplete monolayers, 0 varies with the degree of surface coverage. At the time these experiments were made it was impossible to measure the actual amount of surface coverage, especially since the decrease of the collector concentration in the liquor could be influenced by chemical side reactions. Through the use of the radioactive tracer method for the measurement of the amount of collector adsorbed on the surface of the mineral, Gaudin and Bloecher&apos; were able to determine accurately the actual surface coverage of dodecylamine acetate on quartz, but they did not measure any contact angles. It is believed that the relationship between the surface coverage and the contact angle is extremely important in flotation, especially as Gaudin and Bloecher showed that a 95 pct recovery is possible with a coverage of only 5 pct. Theoretical Considerations The work of adhesion W is the energy bound (in ergs per sq cm) when an interface is formed. It is determined by the difference of the free surface energies (surface tensions) of the respective phases 7j and yZ before contact and the interfacial free surface energy y, after contact. The definition of the contact angle permits the elimination of the unknown surface energy of the solid and hence the calculation of W from the surface tension of the liquid y and the contact angle 8: W = y (1 + COS0) [1] Consider a surface consisting of two components, identified as 2 and 3, 1 being the liquid. The amount of 2 in the composite surface is x, where 0 < x < 1. The respective contact angles with 1 and air are 8, and 8.. The total work of adhesion of such a surface is the sum of the values of the components multiplied by their respective areas. A formal relation can be written: Wm = x-W2+ (l-x)-W, [2] in which W, is the work of adhesion of the composite surface. Eq 1 can be introduced into Wt and Wa, but in the case of W, some discussion is needed. If the two components are segregated, each component forming an integral part of the composite surface there is no physical meaning for a contact angle 8m calculated from W,, by using eq 1. If, on the other hand, the area of each patch of the components is small in comparison with, say, the diameter of the bubble used in measuring, it could be expected that 0m would have a physical significance, because of the action of the surface tension of the liquid-gas interface tending to smooth out sharp corners. How small these patches would have to be is difficult to predict, but by using composite surfaces with microscopically

Jan 1, 1953

By J. R. Lewis, J. H. Hamilton, V. D. Hanson, K. W. Heinlein, J. M.194-000-000-006 Vonfeld, J. P. Denny

TWO overfeed drum-type separators using a suspension of magnetite in water as the separating medium have been installed in the Champion NO. 1 preparation plant of the Pittsburgh Coal Co., Division of the Pittsburgh Consolidation Coal Company. A simplified flow diagram of the Champion No. 1 coarse coal circuit is shown in Fig. 1. A railroad car rotary dump, capable of handling 20 cars per hr, discharges the coal into a hopper. Coal is fed from the hopper of the rotary dump to a 60-in. belt conveyor by two reciprocating pan-type feeders. The belt conveyor feeds the run of mine coal onto the main raw coal screen. The first deck is fitted with 3 in. round hole perforated plate which removes the 3x0-in. coal. The second deck of the screen is equipped with 6-in. lip screens which separate the remaining coal into +6 in. and 6x3 in. The +6 in. coal is transferred to a shaking picking table and then discharged onto the loading boom. The 6x3-in. coal is fed to the No. 2 dense medium vessel for cleaning. The clean coal from this unit flows to a vibrating screen where the medium is removed and the coal sized into 6x4 in. and 4x3 in. The 6x4-in. coal is transferred to the loading booms and the 4x3-in. is conveyed to the clean coal classifying screens to remove degradation. The 3x0-in. raw coal is blended in a system composed of three storage bins having a total capacity of 400 tons. From these bins the coal is fed onto a 48-in. flight conveyor by three reciprocating feeders. This flight conveyor delivers the coal to the Rheo plant. The 3x0-in. coal is then cleaned in two 48-in. Rheolaveur launders each equipped with two Rheo boxes. The first set of boxes removes a primary refuse and the second set produces a middling product which is recirculated in the launders. The cleaned coal and water overflows from the primary launders to two sizing and dewatering shaker screens where the water and — -in. coal are removed for further cleaning in the Rheo fine coal plant. The 3x3h-in. clean coal is combined with the 4x3-in. coal from the No. 2 vessel, sized into 4x2 in., 2x1 34 in., and 1&apos;/4x in., then sent to the loading booms. The 3x0-in. refuse from the primary launders is normally fed to the No. 1 dense medium circuit, but any portion or all of this material can, as an alternate, be processed in the Rheo rewash launder. The primary refuse when fed to the dense medium circuit is screened into YSXO which is cleaned in the fine coal plant and 3x for cleaning in the No. 1 vessel. The clean coal from this vessel is passed over a vibrating drainage and rinse screen, then sluiced to the rewash sizing shaker where it is dewatered and sized for loading. The installation of a pilot plant separating vessel using a suspension of magnetite in water was pro-

Jan 1, 1953

By J. L. Thompson

There are two basic forms of the LPG-slug process: the gas driven and the water driven. The pressure required for miscibility between gas and LPG prohibits the use of the gas-driven LPG process in shallow reservoirs. The water-driven LPG slug process normally exhibits good sweep efficiency. However, displacement of the LPG by water is poor. An improvement in this process appears possible by injecting a slug of carbon dioxide between the LPG slug and the water drive. Laboratory experiments were conducted in homogeneous linear systems to determine the effect of pressure on the various displacement zones. In the carbon dioxide-LPG displacement zone, the effect of pressure on the displacement efficiency is negligible above the miscibility pressure. However, the displacement efficiency decreases linearly with decreasing pressure below the miscibility pressure. With water displacing carbon dioxide, it was found that the recovery of carbon dioxide after water breakthrough can be predicted from its solubility in water. A displacement test was conducted with LPG and carbon dioxide slugs large enough to avoid interference between the oil-LPG, LPG - carbon dioxide and carbon dioxide - water displacement zones. Under these conditions, essentially complete oil and LPG recovery was obtained. However, a substantial amount of carbon dioxide was left in the core at water breakthrough. INTRODUCTION It has been shown in homogeneous linear systems that essentially complete oil recovery can be obtained by displacement with a miscible fluid such as LPG. Economic considerations dictate that the valuable LPG also be recovered. Methods proposed for recovering the LPG include (1) displacement with natural gas at a pressure high enough to make the two fluids miscible1 (the disadvantage of this method is that the required pressure of about 1,500 psi is too high for shallow reservoirs) and (2) displacement of the LPG with water2 (principal disadvantage is that a large amount of LPG remains in the formation because of poor displacement efficiency). This paper treats an improvement in the water-driven LPG slug process3,4 where carbon dioxide is injected between the LPG and water. Carbon dioxide is completely or at least partially miscible with propane and soluble in water; thus, displacement efficiency is improved at both ends of the carbon dioxide slug. To minimize effects of other variables, all experiments were conducted in linear core systems. GENERAL PROCESS DESCRIPTION The displacements of propane by carbon dioxide and carbon dioxide by water are considered separately, assuming enough of each is injected to prevent mutual interference. Displacement descriptions are confined only to the part of the pore volume containing mobile fluids unless otherwise specified. The schematic representation is given in Fig. 1. Starting at the producing well, a zone containing only oil is followed by a zone containing a single-phase mixture of propane and oil. The concentration of propane increases in the direction of the injection well and ultimately grades to pure propane. Then follows a zone containing a mixture of propane and carbon dioxide in continuously varying proportions until 100 percent carbon dioxide is reached. In this zone, the concentration of carbon dioxide in the immobile water phase also varies from zero to full saturation. Whether the displacement of propane by carbon dioxide is of complete or partial miscibility depends on pressure and temperature (Fig. 2). If the horizontal line representing the prevailing pressure intercepts the boundary curves of the phase envelopes for the prevailing temperature (i.e., if the pressure is lower than the critical

By J. H. Hamilton, J. R. Lewis, K. W. Heinlein, V. D. Hanson, J. M. 194-000-000-006 Vonfeld, J. P. Denny

TWO overfeed drum-type separators using a suspension of magnetite in water as the separating medium have been installed in the Champion NO. 1 preparation plant of the Pittsburgh Coal Co., Division of the Pittsburgh Consolidation Coal Company. A simplified flow diagram of the Champion No. 1 coarse coal circuit is shown in Fig. 1. A railroad car rotary dump, capable of handling 20 cars per hr, discharges the coal into a hopper. Coal is fed from the hopper of the rotary dump to a 60-in. belt conveyor by two reciprocating pan-type feeders. The belt conveyor feeds the run of mine coal onto the main raw coal screen. The first deck is fitted with 3 in. round hole perforated plate which removes the 3x0-in. coal. The second deck of the screen is equipped with 6-in. lip screens which separate the remaining coal into +6 in. and 6x3 in. The +6 in. coal is transferred to a shaking picking table and then discharged onto the loading boom. The 6x3-in. coal is fed to the No. 2 dense medium vessel for cleaning. The clean coal from this unit flows to a vibrating screen where the medium is removed and the coal sized into 6x4 in. and 4x3 in. The 6x4-in. coal is transferred to the loading booms and the 4x3-in. is conveyed to the clean coal classifying screens to remove degradation. The 3x0-in. raw coal is blended in a system composed of three storage bins having a total capacity of 400 tons. From these bins the coal is fed onto a 48-in. flight conveyor by three reciprocating feeders. This flight conveyor delivers the coal to the Rheo plant. The 3x0-in. coal is then cleaned in two 48-in. Rheolaveur launders each equipped with two Rheo boxes. The first set of boxes removes a primary refuse and the second set produces a middling product which is recirculated in the launders. The cleaned coal and water overflows from the primary launders to two sizing and dewatering shaker screens where the water and — -in. coal are removed for further cleaning in the Rheo fine coal plant. The 3x3h-in. clean coal is combined with the 4x3-in. coal from the No. 2 vessel, sized into 4x2 in., 2x1 34 in., and 1&apos;/4x in., then sent to the loading booms. The 3x0-in. refuse from the primary launders is normally fed to the No. 1 dense medium circuit, but any portion or all of this material can, as an alternate, be processed in the Rheo rewash launder. The primary refuse when fed to the dense medium circuit is screened into YSXO which is cleaned in the fine coal plant and 3x for cleaning in the No. 1 vessel. The clean coal from this vessel is passed over a vibrating drainage and rinse screen, then sluiced to the rewash sizing shaker where it is dewatered and sized for loading. The installation of a pilot plant separating vessel using a suspension of magnetite in water was pro-

Jan 1, 1953

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

The solubilities of oxygen in liquid Ag-Au, Ag-Pt, and Ag-Pd alloys have been determined in the range of 940° to 1200°C at 1 atm pressure of oxygen using an improved Sieverts technique. The additions of gold (0 to 57 pct), platinum (0 to 27 pct), and palladium (0 to 22 pct) to liquid silver continuously decrease the solubility of oxygen in liquid silver. Activity coefficients and interaction coefficients of oxygen in these alloys and have been calculated. The interaction coefficientscan be described by the following equations: Approximate second-order interaction coefficients (pM have been calculated. The contribution of the product, pMxNM, to In yo only becomes significant at high alloy concentrations. RECENTLY several investigators1"3 have redeter-mined the solubility of oxygen in liquid silver. In general the recent findings1" for Po, = 1 atm are in good agreement with the equation:4 log %O = 695.4/T + 1.086 [1] It is established1, 2 that the solubility of oxygen follows Sieverts&apos; law reasonably well, at least up to 1 atm partial pressure of oxygen. It should be noted that a very slight deviation from Sieverts&apos; law has been reported by Lupis and Elliott.3 Only recently has the solubility of oxygen in Ag-X binary liquid systems received much attention, and only the Ag-Cu, Ag-Au, Ag-Pt, and Ag-Pd systems have been studied. Par lee, Sacris, and zoellners reported that the solubility of oxygen in liquid silver increases progressively with the small additions of copper (0 to 0.5 pct) up to the point where the copper oxide phase appears. Lupis and ~lliott~ have reported that the solubilities of oxygen in liquid silver decrease progressively with the additions of gold, platinum, and palladium. However, their investigation was limited to 0 to 5 pct of these alloying elements, a range too limited to satisfy the requirements of the research program of this laboratory, where the solubilities of oxygen in the range of 0 to 30 pct were required for the calculation of chemical diffusion coefficients of oxygen in these alloys. The present paper deals only with the solubilities of oxygen in these alloys while another paper will deal with the diffusion of oxygen in these alloys. EXPERIMENTAL METHOD A Sieverts technique was employed which involved an improved design of the reaction tube, Fig. 1, as described briefly in a previous communication.4 Liquid melts (70 to 100 g) were held in Norton Alun-dum crucibles. The induction furnace used had a maximum output of 2.5 kw with very fine control. This induction system had excellent stability and the final equilibrium temperatures measured by calibrated Pt-Pt, 10 pct Rh thermocouples are believed to be within ±2C. These thermocouples were checked against the melting point of pure gold wire, and the results agreed with standard tables (±l°C). Each run involved a careful sequence of operations. The sample was heated to and held at about 900°C in vacuum for 3 to 4 hr with the thermocouple in a retracted position. After melting, the melts were usually exposed to a small amount of oxygen (0.5 to 2.0 cu cm) and then degassed slowly for 1 to 2 min to remove any oxidizable volatile impurities such as carbon and sulfur as CO, CO2, SO2, and SO forth. Argon gas was then allowed to enter the system. The protection tube containing the thermocouple was then

Jan 1, 1969

By W. M. McCardell, W. O. Winsauer

The abnormal conductivity found in shaly reservoir rocks containing an electrolyte is shown to be a consequence of the electrical double layer in the solution adjacent to charged clay surfaces. This increased conductivity results from a higher concentration of ions in the double layer than in the solution in equilibrium with the double layer. It is shown that the magnitude of the increased conductivity of a shaly reservoir material is influenced by the concentration and type of ions in the equilibrium solution as well as by the colloidal nature of the rock. INTRODUCTION An important factor in the quantitative interpretation of the electric log is the resistivity factor of reservoir rock. The resistivity factor is defined as the resistivity of the rock when completely saturated with an electrolyte divided by the resistivity of the electrolyte itself.&apos; In the normal case, the resistivity factor for a particular rock sample is independent of the resistivity of the electrolyte and reflects the pore geometry of the rock.&apos; In 1949. Patnode and Wyllie&apos; showed that in some cases the resistivity factor is not constant, but instead varies with the resistivity of the electrolytic solution. It was shown that clean sands behave normally—i.e., that the resistivity factor does not vary with resistivity of the electrolyte — but that sands con- taining shale and clay may exhibit abnormally low resistivity factors when the solution used to saturate them is of fairly high resistivity. At low resistivities of the electrolyte, the resistivity factor for a shaly sand appeared to approach a normal behavior. It is evident that the resistivity factor of a shaly sand is dependent upon factors other than pore geometry when the solution used to saturate it is of high resistivity. Patnode and Wyllie, and later de Witte,&apos; assumed that the conductivity of a shaly sand saturated with an electrolyte could be represented as the sum of two quantities. One of these was assumed, in effect, to be the conductivity which would be expected if the sample were a clean sand. and the other was assumed to be a conductivity inherent in the sample itself. The latter was supposed to be constant for a given rock sample regardless of the solution used to saturate it. The source of this added conductivity was ascribed to "conductive solids." In actual practice: the effect of the abnormal behavior of shaly sands is of minor importance except when the resistivity of a formation such as a sand is high. Thus the effect is more important when the sand is saturated with a dilute brine than when it contains a more concentrated electrolyte. The effect is also more important when the sample contains oil or gas than when it contains only saline water. Recently it has been suggested that the porosity of a stratum may be estimated from the electric log by use of the resistivity of the invaded zone." This is the zone flushed with the filtrate from mud used in drilling the well. which is ordinarily very dilute brine. When the method is applied to shaly sands, the effect of abnormal conductivity becomes of importance. This report describes an investigation of the mechanism responsible for the abnormal behavior of the resistivity of shaly rock saturated with conducting solutions. The investigation

Jan 1, 1953

By G. W. Nabor, H. J. Ramey

A blotter-type electrolytic model was utilized to prepare flow diagrams for a field test of the in-situ combustion process. It is pointed out that the areal sweep of a combustion pattern is similar to sweep patterns that would be developed at an infinite mobility ratio, which exists (approximately) across a combustion front because of the complete removal of liquids from the sand behind it. The precision of the blotter method was tested by comparison with results obtained by other techniques and was found to be satisfactory. The blotter-type model will not furnish as much information as more elaborate and expensive potentiometric models, but its speed of operation and ease of construction make it a highly satisfactory tool to determine areal sweep patterns. A tabulation of sweep efficiency and mobility ratio is furnished for various well geometries. INTRODUCTION In connection with the first field experiment with the in-situ combustion method of oil recovery," flow diagrams for the unique well geometry and boundary conditions involved in the subject test were developed. From these diagrams, information concerning the areal sweep and distribution of flow was obtained. A survev of the literature on potentiometric models, utilized to solve two-dimensional flow problems,1,2,3,4,5,6,8,9,10 indicated that the information desired could be obtained by means of a blotter-type model by making certain modifications in the technique. The following discussion describes the application of the modified blotter-type electrolytic model to the solution of the problem of the flow of gases in an oil reservoir for an engineering appraisal of the progress of the combustion front during the first field experiment. Considerable information has been published on the theoretical aspects of electrical model techniques. One author stated that:&apos; "The models are based on the observation that since the velocity of an ion in an electrolytic system is proportional to the potential gradient, just as the velocity of a fluid particle in a porous medium is proportional to the pressure gradient, the paths of the ions in the electrolytic systems must be similar to those of the fluid particles in a porous medium with the same geometry and equivalent boundary conditions." This suggestion of a real analogy has been established repeatedly by comparisons of analytic derivations with model results. The analogy between the movement of a combustion front and the model results is not as apparent, since the combustion process differs from water flooding and gas cycling in that the velocity of the burning front is different from the velocity of the injected fluid at the front in combustion. Analogy between electric current flow and movement of the burning front exists because the local velocity of the burning front is proportional to the air (mass) velocity at this point (assuming frontal temperatures are at least as high as the ignition temperature of the fuel). Most model studies fall into one of two categories: (1) electron conduction, or (2) ionic conduction models. Examples of these are models which employ as flow media either a thin metal sheet, or a porous blotter saturated with an electrolyte, respectively. Of the two, the porous blotter model, an ionic conduction model, appears to be the most adaptable to the flow problem that results when using in-situ combustion. This problem requires that the mobility of the particles in the model be controlled analogous to the mobility of gas flowing through burned sand of high permeability to gas and then through oil sand of lower permeability to gas. Although the blotter model has heretofore been

Jan 1, 1955

By Irving B. Cadoff, Ernest Levine

The fracture path in a Cu-4 pct Ag alloy wet with mercury was found to he dependent on the heat treatment used prior to tensile testing. Both quenched and slow-cooled alloys were embrittled by the mercury.. For quenched alloys, which were single -phase, the crack path was intergranular. Slowly cooled alloys, which contained precipitate platelets, exhibited transgranular fracture. By comparing stress-strain data for these alloys with similar data on mercury -embyittled solid-solution alloys, it was found that the role of the precipitate and that of the grain boundary in the fracture process were equivalent . THE fracture path which results when metals are strained in a liquid environment appears to be dependent upon the nature of the specific system. Mixed transgranular and intergranular cracking has been observed in the 2024 T4 aluminum alloy when wet with a Hg-Zn amalgam.&apos; Transgranular fracture was induced in an A1-4 pct Cu alloy by masking off the grain boundaries from the liquid Hg-Zn amalgam.&apos; The embrittlement of solid-solution alloys of copper in mercury results in intergranular fracture.&apos; The effect of a precipitated phase on the fracture path in copper alloys is the subject of the present investigation. Cu-4 pct Ag was chosen so that its behavior could be compared with previous work on embrittlement of copper alloys. PROCEDURE High-purity copper (99.999 pct) was used as a base metal, along with 99.999 pct purity silver. Melting was carried out in graphite crucibles with manual agitation to get adequate mixing. The ingots were homogenized by means of vacuum annealing, chemically cleaned, and cold-rolled with intermediate vacuum anneals, to the desired thickness of 0.025 in. The rolled sheets were sheared to the final specimen size of 1 by 0.025 by 0.1 in. The specimens were then electropolished in phosphoric acid (concentrated) and heat-treated in an evacuated capsule at the solution temperature of 770°C. One batch was slow-cooled and the other quenched in water. The thermal etching which occurred during heat treatment was sufficient to permit grain boundary and precipitate delineation. Tensile tests were carried out in air and in mercury on a Table-Model Instron at a pulling speed of 0.2 in. per min. Wetting was accomplished by electro-polishing in phosphoric acid, rinsing in alcohol, and immersing in a pool of mercury. Once wet the coating was stable throughout the mechanical tests. In our studies it was found that wetting the surface or total immersion in mercury produced identical results. For convenience, the wetting technique was used for the experiments described. The crack pattern was observed directly on the surface by removing the mercury after testing. De-wetting was accomplished by flame heating the samples in a vacuum after testing and before observation of the surface. No etchant or polishing was used so as not to obscure the crack pattern on the surface. The mercury removal, however, resulted in a pitted surface but otherwise left the pertinent features visible. Photomicrographs were taken in this condition so as not to disturb the structure associated with the crack pattern. The average precipitate spacing was measured previous to coating the sample with mercury by use of an optical eyepiece micrometer. RESULTS The microstructure of the quenched specimens was single-phase while that of the slow-cooled specimens contained thin platelets of a second

Jan 1, 1964

By John P. Huger

me phase diagram for the system Ag-Si has been established by thermal analysis. The diagram is a simple eutectic type with a eutectic at 3.0 pct Si and 840°C. From the liquidus curve and with the aid of regular solution theory, the thermodynamic properties of the liquid Ag-Si system at 1420 °C have been determined. Silicon exhibits positive deviations from Raoultain behavior at all compositions, while silver exhibits both positive and negative deviations. MEASUREMENTS of silicon activities in liquid iron alloys by means of distribution studies between the immiscible liquids silver and iron have been reported by Chipman, Fulton, Gokcen, and caskey.&apos; The applicability of this technique is dependent, however, on the accuracy of the silicon activity values in the Ag-Si alloys, particularly in the dilute silicon region. Darken and Gurry2 have shown that log ?si/(1-xSi)2 is approximately linear with composition, but uncertainty exists in the extrapolation to dilute solutions. Their calculations are based on the old Ag-Si phase diagram of Arrivaut3 and any variation in the position of the liquidus curves will strongly influence the extrapolation. The purpose of this study is to redetermine the Ag-Si phase diagram and calculate the associated thermodynamic properties. EXPERIMENTAL The Ag-Si phase diagram was determined by thermal analysis of liquid alloys. The alloys were contained in a 35 mm alumina crucible under a protective stream of purified argon. The crucible was placed inside a 64 mm alumina tube fitted with a gas-tight, water-cooled, copper head. The tube and assembly were heated in a manually controlled globar furnace. The temperature was measured with a Pt, Pt + 10 pct Rh thermocouple in a high-temperature porcelain protection tube. The thermocouple calibration4 was checked against the melting point of pure silver at the start and during the course of the experiments, and against both gold and silver at the completion of the experiments. The alloys were prepared from granular silver analyzing 99.95 pct Ag and powdered silicon analyzing 99.88 pct Si and 0.026 pct Fe. Approximately 150 g of alloy were used for each run. The composition of the alloy was determined by withdrawing samples of the liquid alloy with a vycor tube-aspirator bulb device. Analysis of solidified samples agreed, for alloys containing less than 23 pct Si, within ±0.3 pct Si of the calculated composition. Duplicate samples showed a variance within 50.05 pct Si of the mean analysis. The alloy was heated to 100&apos; to 20pC above the estimated liquidus temperature and then the furnace was adjusted to give an average cooling rate of 2" to 7°C per min. A cooling curve was obtained by taking potentiometer readings at 15-sec intervals. Several analyses were made by recording the thermocouple output on a high-speed, Stip-chart recorder, with the exception of run NO. 11, a minimum of two thermal analyses were made for each alloy and the cooling curves then obtained duplicated the liquidus and eutectic temperatures to about 1°C. RESULTS The results of the thermal analysis are given in Table 1, and are represented as the Ag-Si phase dlagram, Fig. 1. The eutectic composition was found

Jan 1, 1963

By S. R. Goodman, Hsun Hu, R. S. Cline

The quenching technique has been used to study phase relations in the composition area 2FeO.SiO2-FeO-SiO2-MnO.Si02-ZMnO.SiO2 of the system iron oxide-manganese oxide-silica under strongly reducing conditions such as exist in a gas mixture consisting of equul parts of carbon dioxide and hydrogen. Liquidus and solidus temperatures of most mixtures in the composition area studied are in the range of 1173° to 1345°C. EQUILIBRIUM relations existing among the oxides of iron, manganese, and silicon are of particular interest in two areas of steelmaking: slags and ingot inclusions. Mixtures of these oxides represent about 90 pct of the slag in the acid steelmaking process, and so dominate the chemistry of the whole refining process. These constituents also play an important role in the early slags existing at the time of the "lime boil" in the basic open hearth process. If these slags are liquid, they "wet" the lumps of lime rising from the bottom of the bath, and react with them. A liquid slag rich in CaO is then formed at the very beginning of the refining. Because the temperature is still low, all conditions for a good dephosphoriza-tion are fulfilled at this stage of the operation. Metal deoxidized with ferromanganese or silico-manganese is likely to contain, as inclusions, phases made up from among the oxides of iron, manganese, and silicon. A knowledge of stability relations existing among the phases present in this system, therefore, enables one to predict the hardness of the inclusions encountered. Moreover, because the shape of the inclusions in steel has a profound influence on the physical properties of the metal, it is important to establish whether or not the oxidic material is present as liquid or crystalline phases during heating and rolling of the steel (-1150 to 1350°C). A knowledge of melting relations in synthetic mixtures of iron oxide, manganese oxide, and silica will give a clue to these problems. Methods for determining such relations and the results obtained are described iln this paper. I) PREVIOUS WORK A number cf previous studies have dealt with the three "binary"* systems bounding the system iron oxide-mangar,.ese oxide-silica. The system iron oxide-silica was studied by Bowen and shairerl in 1932. Their data were obtained by equilibration of mixtures in contact with metallic iron. Phase relations for the system iron oxide-silica ill atmospheres of different oxygen pressures car1 be derived from data on the system FeO-Fe2O3-SiO2 as determined by Muan.2 The diagram shown iri Fig. l is a section of this system in an atmosphere of CO2 and H2 in ratio 1:l. The system manganese oxide-silica has also been the subject of several investigations. Most of the early studies suffered from a lack of proper control of the atmosphere under which the equilibrations were carried mt. Phase diagrams for the system at two well defined levels of oxygen pressures have been determined recently. Glasser3 determined stability relations in an atmosphere consisting of carbon dioxide and hydrogen in ratio 5:1, diagram Fig. 2, and Muan4 studied phase relations in the system in air.

Jan 1, 1962

By H. J. Beach

This paper describes the properties and uses of cementitious mixtures containing 10 to 20 per cent bentonite and 2 per cent or more sodium chloride. Salt additions improve bentonite cement by increasing early strength and stabilizing viscosity without changing thickening time. The volume yield of cement is increased 20 per cent or more without lowered early strength. The unique properties of salt in this type of system make savings of more than 10 per cent possible where light-weight, low-strength cementitious material is adequate to fill behind pipe. The density range of these mixtures is 12 to 13 1b/gal and the filtration rates are medium-low, aiding the placement of long columns in primary cementing. Where available, sea water is an ideal salt source in preparing these slurries. INTRODUCTION Accelerators increase the rate of cement hydration. In speeding reaction with water, they can affect cement performance by reducing thickening time and increasing early strength after set. Accelerators that cause both effects can be considered "total", and those which produce only one effect can be called "partial". Materials that act conversely to accelerators are retarders. and they also can be total or partial. Partial retarders. make high-temperature cementing possible by prolonging thickening time while impairing early strength only slightly. Most known accelerators are total. A useful partial accelerator would increase strength without altering thickening time. This report concerns material combinations in which a normally total accelerator exerts unique partial properties. Utilizing these limited effects improves bentonite cement. SEPARATE EFFECTS OF SODIUM CHLORIDE AND BENTONITE ON CEMENT Sodium chloride and calcium chloride are commonly used in cement, and at low concentrations their effects are similar. Ludwig1 studied sodium chloride in API Class A and Class E cements.&apos; Figs. 1 and 2 sum- marize his data taken at 140°F on slurry pumpability and early strength. Normal water-to-cement ratios are 0.46 and 0.40, respectively, for Class A and Class E cements. At saturation the salt content is 12 to 14 per cent of the weight of cement solids. The illustrations, therefore, cover the range of salt solubility in the mixing water. The data show that sodium chloride is a total accelerator of the Class E cement studied over the range of solubility. It is total in Class A cement to 6 per cent. Above this concentration salt becomes a retarder— partial from 6 to 10 per cent and total above. These results are general for different brands of Class A cement, although the shift from acceleration to retardation may occur at different salt concentrations for different temperatures. The results are specific for the Class E brand studied. In discussing his data, the investigator emphasized that different Class E cements might respond erratically to salt, depending on the brand chosen. Morgan and Dumbauld3 escribe the properties of bentonite cement in a paper that is a standard reference in using these systems. Bentonite functions in cement as an enabling agent; each bentonite addition equal to 1 per cent of the weight of dry cement makes possible the further addition of 4.5 per cent water.&apos; Thus, 10 per cent bentonite in Class A cement, normally slurried neat with 46 per cent water, enables the slurry to contain another 45 per cent before settling. Water is one of the lightest and cheapest cement extenders; it reduces density and cost. Bentonite cements produce uniform slurries having low susceptibility to solids separation. After set, they offer low resistance to perforation.

By S. Leber

Pole figures and pole distributions were used for the quantitative detevinination of the preferred orientations in swaged tungsten rods and the effect of subsequent wire drawing on the texture. In the swaged rod, the preferred orientation could best be described as a pseudo (111-112) [110] cylindrical texture. A secondary component was assigned the indices (110) [001]. Further reduction by swaging retained these cylindrical textures. Wire drawing caused lattice rotations about the wire axis, converting the cylindrical texture into a normal fiber texture. The conversion was initiated and proceeded lnost rapidly in the center of the wire. The (110) /001] component was converted into a (110) fiber texture by wire drawing. The effective rotations were about axes contained in the lransverse plane. The preferred orientation associated with tungsten wire usually has been assumed to consist of a (110) fiber texture. This implies rotational randomness around the wire axis. Leber1 has shown that rotation about the wire axis may be restricted resulting in a preferred orientation designated as a cylindrical texture. Specific crystal planes tended to remain aligned parallel to the wire surface. This texture seemed to be the result of the swaging operation used in the intermediate stages of fabrication. Bhandary and cullity2 detected similar textures in swaged iron wires. Peck and Thomas3 suggested that the preferential alignment of crystal planes parallel to the wire surface was the result of tangential flow, characteristic of swaging. Wire drawing, following swaging, twisted the crystals about axes parallel to the wire axis, converting the cylindrical texture into a normal fiber texture.4 In this investigation, quantitative techniques were used to more accurately characterize the cylindrical texture and to study its conversion into a normal fiber texture. PROCEDURE The material investigated was lamp-quality tungsten. Three ingots were rod-rolled and swaged to 112 mils diameter, and were then drawn to 10-mil wire. Samples were obtained after each drawing pass. (110) and (200) pole figures were obtained from samples prepared as shown in Fig. 1. To form the sample shown in Fig. l(a), l-in. lengths of wire were glued side by side to form a l-in. square. The composite was ground and electropolished to form a diametral reference surface. For certain specific tests, samples were prepared as shown in Fig. l(b). This composite was made from 10-mil-thick strips prepared by grinding on parallel longitudinal planes. The polished reference surface in this case was, in essence, the wire surface. The two forms of samples [~igs. l(a) and l(b)] were related by a 90-deg rotation around the wire axis. Because of ease in preparation, most data was obtained from the diametral samples. The X-ray data were obtained using a Siemen&apos;s pole-figure goniometer. These data were not corrected for absorption or defocusing effects, since only the angular locations of the intensity maxima were of interest. Regions of the pole figure more than 80 deg from the center were not investigated. Partial monochromatization was achieved by the use of unfiltered copper radiation and a krypton-filled proportional counter. No evidence of spurious white radiation effects5 could be detected. Therefore, more elaborate X-ray techniques were not required. Intensity levels were chosen to show all pertinent details of the orientation distributions. The reference plane for the pole figures was the diametral section. The orthogonal reference directions, shown in Fig. 1, were the wire axis, the radial axis per-

Jan 1, 1965

By J. P. Heller

The purpose of this discussion is to comment briefly on one of the points raised in the paper. The topic is that referred to in the Conclusion 2, in which the authors note a "disproportionate increase in mixing rate" as they proceed from a displacement performed at viscosity ratio 0.998 to one at 1.002. The recovery curve of this displacement, Fig.2A, shows a quite noticeable difference between the two runs in which displaced and displacing liquids were interchanged. This difference is ascribed by the authors to the change in viscosity ratio between the two experiments. This interpretation of the experimental results must certainly be based on rather precise measurements of the fluid viscosities or, at least, of the ratio of their viscosities. The ordinary Ostwald viscometer, employed in the usual way, is only just able to distinguish between liquids whose viscosities differ by two or three parts per thousand. The experimental refinements which then must have been necessary to measure with any precision a viscosity ratio of 1.002 would be worthy of mention. Indeed, one would have expected the authors to devote at least a paragraph to the display of this technique. For the same reason - to emphasize that the details of such unusually critical experimental work should be reported and discussed in the literature — I would have liked to see some comment by the authors on the requirements for temperature control during both the viscosity measurements and the displacement experiments. The temperature coefficient of viscosity of Soltrol C at room temperature has been measured in this laboratory at about - 1.9%/1°C. How much did the coefficients for the fluid mixtures used in the experiment differ from this and from each other Even if the two fluids were identical in this respect, it would appear that a temperature difference of .l°C between them in the flow system would produce a viscosity con- trast equal to that imposed by their composition. Reference to the experimental solutions of these problems would render Conclusion 2 more credible. Published theoretical work on the stability problem contains no indication of such extreme sensitivity to the viscosity ratio in the immediate neighborhood of unity. On the contrary, perturbation calculations such as those made by Chuoke1 and Perrine2 lead to initial finger growth rates proportional to the first power of the viscosity difference. The later instability growth calculated by Scheidegger,3 using the assumption of zero pressure gradient perpendicular to the average flow, is also simply proportional to the viscosity difference. The conflict regarding the sensitivity of the dependence of instability growth or mixing rate on the viscosity contrast needs explicit recognition in the literature. In particular, it would seem that the experimental work reported here should be supported by a more detailed description of the viscosity controls. Further discussion of possible alternative interpretations of the data would also be in order. For instance, is it possible that the unconsolidstted bead pack used changed its characteristics between the runs (due, perhaps, to the handling and inverting involved in the injection of the front) Or, are the data points of Fig. 2A averages from several runs performed in a series in which the two liquids alternated as displaced and displacing fluids? To summarize, it seems to me that the relationship asserted by Conclusion 2 in the paper needs the support of more detailed experimental evidence. REFERENCES 1. Chouke, R. L., van Mews, P. and van der Poel, C.: "The Instability of Slow Immiscible Viscous Liquid-Liquid Displacements in Porous Media", Trans., AIME (1959) Vol. 216, 188.

By L. K. Nemeth, H. T. Kennedy

The investigation presented in this paper was performd to develop a relationship between the dewpoint pressure of a hydrocarbon reservoir fluid and its composition, temperature and characteristics of the heptanes-plus fraction. This is part of an over-all program to develop correlations for the essential properties of reservoir fluids with the composition, temperature and pressure. In all, 579 dewpoint pressures, determined experimentally on 480 different condensate systems along with their compositions and temperatures, were obtained from the literature and from previously unpublished sources. Compositions were expressed in terms of mol fractions of methane through heptanes-plus, nitrogen, carbon dioxide and hydrogen sulfide, and the molecular weight and specific gravity of the heptanes-plus fraction. Distribution of the samples assured a good representation of most of the major oil-producing areas in the world. A multiple regression analysis program written for the IBhl 7094 digital computer was used to compare numerous equations and to calculate their coefficients. The final equation containing 11 coefficients resulted in an average absolute deviation of 7.4 percent for all the samples. Segregation of data on the basis of one or more variables did not materially improve the results. The correlation developed is useful in predicting the dewpoint pressure of condensate reservoir fluids from variables normally measured in the laboratory. INTRODUCTION In any discussion of the dewpoint of hydrocarbon mixtures, it should be noted that there are two kinds of dewpoints which must be distinguished. The first type, or normal dewpoint, usually occurs at low pressures as dry gas is compressed to the point where liquid first forms. The second type, sometimes called the retrograde dewpoint, occurs when a gas mixture containing heavy hydrocarbons in solution is depressured until a liquid is formed. The first type, as applied to condensate mixtures, would normally be below atmospheric pressure and would be of no interest in reservoir performance. The second type is of great significance in interpreting reservoir behavior and is the property referred to throughout this paper. Laboratory measurement of dewpoints is laborious, expensive and subject to many errors, and it is desirable to find a reasonably accurate method to predict dewpoint pressures from the composition and other readily available properties normally measured on the fluids. A possible method of calculating dewpoint pressures would be to employ a set of equilibrium ratios (K-values). 1 However, the K-values themselves depend on composition as well as temperature and pressure; presently their use adds nothing to the accuracy of predicting dewpoints. If future correlations provide a significantly better method of estimating K-values for heavy hydrocarbons, they may be of greater use. REVIEW OF LITERATURE In 1944, Olds, Sage and Lacey 2 studied the behavior of fluids from the Paloma field. Properties of seven mixtures were studied at temperatures ranging from 100 to 250 F and at pressures up to 5,000 psia. From the information obtained, the influence of composition and temperature upon the dewpoint was determined. It was found that removal of the intermediate molecular weight components from the mixture resulted in considerable increases in the dewpoint pressures. Results indicated that the effect of changes in temperature was relatively minor when compared with the effect of modifying the mixture by removing the intermediate components. Thus, removal of propane and butanes resulted in an increase in dewpoint pressure more than 10 times greater than a change in temperature from 100 to 250 F. The authors stated that althouah

By Fred H. Poettmann, J. K. Welchon, A. F. Bertuzzi

A series of gas-lift tests was made which verified conclusions reached from previous studies and which showed that gas-lift performance could be calculated if reasonably accurate data on the producing characteristics of the well are available.&apos; The test installation is described. Its essential features consisted of a rate-of-flow controller to regulate the input gas and an auxiliary string of small diameter tubing to conduct the input gas to the point of injection in the eductor tubing. In general, it was shown that for continuous gas-lift operation, injection should be as deep as possible consistent with available gas pressure and rate of production desired. Calculated curves are presented which completely characterize the gas-lift performance of the well tested. INTRODUCTION A correlation based on field data from a large number of flowing and gas-lift wells, covering a wide range of oper- ating conditions, was developed which permitted the logical design and prediction of the performance of continuous gaslift installations.&apos; The procedure made it possible to calculate the depth, pressure, rate at which to inject gas, horsepower requirements, and the effect of production rate and tubing size on these quantities. As a result of these calculations certain significant facts were brought to light or re-emphasized. The presence of efficient ranges of operation and an optimum injection depth for a given rate of production were shown to exist as well as the fact that the lower the tubing pressure the less the horsepower requirements to lift the reservoir fluids. The fact that the gas lift performance can be predicted by calculation does not mean that any given installation will perform over the entire range predicted. Many of the conventional continuous gas-lift installations will not permit operation over the entire range predicted by calculation (particularly in the efficient range of operation) because of the performance characteristics of the installation. Consequently, field tests were initiated for the purpose of investigating and arriving at a simple continuous gas-lift installation which would operate under all conditions predicted by calculation. The first series of tests involved the use of mechanically operated valves. These valves were slip-joint type valves which are opened and closed by lowering or raising the tubing at the surface by means of a hydraulic jack. These valves were chosen because it was hoped that they could be opened or closed at will and did not depend on the gas pressure in the annulus or the pressure of the fluid in the tubing for their operation. Unfortunately, the valves did not operate satisfactorily and it was imossible to open or close each valve at will. Some limited data were obtained, however, which verified the predicted benefits resulting from the use of lower tubing pressures. In the next series of tests the valves were removed and the gas was injected from the annulus through a 14/64-in. orifice equipped with a reverse check valve. A packer was set below the valve to seal off the space between the 2-in. tubing and 5-in. casing. The injection point was located at 3,810 ft. This arrangement provided satisfactory mechanical operation. However, it was impossible to obtain low rates of liquid production at low tubing pressures as predicted by calculation. A minimum gas injection rate existed below which steady flow was impossible. Liquid pro-

Jan 1, 1953

By C. A. Bruch, W. E. McHugh, R. W. Hockenbury

Commercially pure molybdenum specimens were irradiated in the Materials Testing Reactor for an estimated exposure of 1.9 to 5.9x10 20 thermal nvt. Prior to irradiation, the material was ductile in the tension test; whereas after irradiation, it was brittle. The results of tension tests conducted at various temperatures revealed that the transition temperature for this material had been increased from —30&apos; to +70°C as a result of the radiation exposure. From metallographic studies, it is concluded that the embrittlement is due to submicroscopic changes which raise the flow stress-temperature curve of the material. PRIOR to ten years ago, the bombardment of metals with high speed heavy particles such as protons, deuterons, a particles, and neutrons was primarily of academic interest. These particles existed in extremely small numbers in a few laboratories and only under very special conditions. With the introduction of the nuclear power reactors, these particles are now available in enormous quantities and it has become important from a practical standpoint to learn how well metals withstand severe reactor radiations. The principal radiations of concern in reactors are neutrons and y rays, since the heavier charged particles exist only in limited regions of reactors. Seitz,&apos; in a theoretical approach, has shown that all of these high energy particles, except y rays, have enough energy to knock atoms from lattice sites and that these knocked-on atoms have enough energy to cause additional displacements of neighboring atoms. The result of this process would be a lattice containing many imperfections in the form of interstitial atoms and vacancies. Hence, it would be expected that the properties of metals can be changed by reactor radiations, and such has been found to be the case. Only a limited amount of data have been published in the open literature,2,3 and these data have been for relatively low integrated-neutron-flux exposures. In general, one effect of reactor radiations on the mechanical properties of metals has been to increase strength and decrease ductility. It is now possible to irradiate specimens in the Materials Testing reactor at much higher fluxes and to higher integrated exposures than previously possible.&apos; The data which are being presented here describe the effects of a relatively high exposure on some mechanical properties of molybdenum. Experimental Procedures Material: The molybdenum used in this investigation was obtained from the Climax Molybdenum Co. The two heats from which the material originated were melted under a vacuum of 5 to 30 microns and cast in 7 in. diam water-cooled copper molds. One ingot contained 0.061 pct C and the other 0.066 pct. Both ingots were hot worked by extrusion and rolling into % in. diam rods, after which they were annealed and straightened. The rods were subsequently heated to 1100°C in a hydrogen atmosphere and swaged to ½ in. diam rods at the Research Laboratory of the General Electric Co. The resulting material had an average hardness of 264 VPN, or 99.2 Rb, and had an average of 5000 grains per sq ml in the transverse section, Test Specimens: Substandard-size tensile specimens were prepared according to the specifications shown in Fig. 1. These specimens were used also for hardness measurements. The metallographic specimens were small disks which were polished, etched, and photographed at X1000 prior to irradiation. The field studied was

Jan 1, 1956

By R. M. Rose, D. P. Ferriss, J. Wulff

Single crystals of tantalum were grown by multipass zone melting in an electron beam apparatus. Tension tests of these crystals at 4.2 x 10&apos;* per sec-gave a resolved louler yield stress of 7300 psi at with a chisel edge; total uniform deformation increased from 1 to 2 pct at 77°K to over 20 pct at 300°K. This, and slip traces, indicated that deformation is more inhomogeneous at lower temperatures. Deformation occurred exclusively by slip in <III> directions, on planes in the <111> zones. Cross slip was frequent, particularly for those orientations where the resolved shear stress on the cross system was comparable with that on the primary plane. The existence and magnitude of the upper yield point were found to be sensitive to orientation. This effect was related to the circumvention of dislocations which were "locked" by interstitial atoms, by double cross slip, or composite slip, of screw dislocations. Prestrainirg at 300°K did not remove the upper yield point in subsequent tension at 77°K. Also, this treatment was found to cause yield points, where none existed for the unprestrained material. This behavior was also rationalized in terms of the circumvention mechanism. The mechanical properties of polycrystalline tantalum have been investigated by several workers,1"4 and may be summarized by pointing out the following features: a) Sharp rise of yield stress with decreasing temperature below room temperature. b) Response to strain aging at 300" to 400"C. c) Yielding with upper and lower yield-point phenomenon at and below room temperature. d) Low strain hardening below room temperature. e) Reluctance to twin except at very high strain rate. Furthermore, tantalum is ductile at ordinary strain rates as low as 4.2"K.&apos; This feature, in particular, makes tantalum unique among the high melting point, bee transition metals of Groups V and VI in the periodic system. Therefore, a more fundamental and detailed knowledge of the low-tempera- ture deformation of tantalum is required. Since high purity and the absence of grain boundary effects make such a study most productive and unambiguous, the method of electron beam zone melting was selected for the preparation of test specimens. This technique has the further advantage that crystals may be seeded in order to obtain any desired orientation. EXPERIMENTAL The electron beam zone-melting equipment was constructed as a modification of that described by Calverley, Davis, and Lever? All crystals were made by three passes of the molten zone at 4 mm per min to achieve an optimum purity commensurate with economy of time and material. Table I reports the chemical analyses of the starting and refined metal. It will be noted that there remain some 50 to 70 wt ppm of interstitial elements, while all substi-tutional elements have been removed by evaporation. Tungsten is picked up by evaporation of the cathode filament wire. Crystal seeding was normally successful within 3 deg, and the orientation of all crystals are given in the standard stereographic triangle in Fig. 1. Tensile bars were prepared from the crystals by centerless grinding to the shape in Fig. 2. Specimens were then electropolished to remove 10 pct of the diameter in order to remove worked material and to prepare a metallographic surface for subsequent deformation trace observations. All specimens were held in the split bushing grips as indicated in the cross section view of Fig. 2. All tests were made at a strain rate of 2 112 pct per min in an Instron testing machine.

Jan 1, 1962