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By John J. Egan, A. B. Kinzel, Walter Crafts

The demands of the petroleum and chemical industries for steels to be used in pressure vessels and similar structures at artificially low temperatures are continually increasing, and the writing of proper specifications with suitable tests becomes increasingly important. Likewise, the selection of suitable steels for such applications is of increasing concern to the metallurgist. It is generally recognized that highly alloyed steels of the austenitic stainless type retain their properties even at very low temperatures and represent the best technological solution of the low-temperature steel problem. However, in many instances less expensive carbon or low-alloy steels suitable for service within limited temperature ranges are available. The problem thus becomes one of defining the various factors involved in the production and fabrication of these less expensive steels and determining the temperature ranges in which their properties justify engineering application. Most of the applications involve welded structures, and the heat effect of welding as well as the nature of the weld metal are matters of prime concern. The first problem that the metallurgist faces is the determination of the type of test to be used as a criterion of the performance of the steel in low-temperature service. It has been generally recognized that the static properties of steel as determined in the ordinary tensile test undergo a gradual and relatively slight change as the temperature of test is lowered in the range of current interest; i.e., from room temperature to minus 120' C. It is further generally recognized that the behavior of steel under impact involving notch sensitivity is definitely affected at the lower temperatures. While the major subject of this paper is the effect of grain-refining deoxidizers, of low-alloy additions and of welding on the low-temperature notched-bar impact properties, an inquiry into the general behavior of steel under low-temperature impact testing is included. This is a pertinent portion of the investigation and the results thereof are

Jan 1, 1937

By James T. Gow, Oscar E. Harder, Anton de S. Brasunas

THIS paper deals with the results obtained and the techniques employed in determining: I. Liquidus and solidus temperatures of the HH and HT type heat-resistant alloys. † 2. The relation of true temperatures (thermocouple) to apparent temperatures (optical pyrometer) for the molten HH and HT type alloys. This work was the outgrowth of needing to know something definite about these temperatures in order to study the effect of pouring temperatures, shake-out times, and heat-treatments on the properties of some heat-resistant alloys. The information developed is thought to be of interest to industry for guidance in foundry practices and the industrial heat applications of the alloys. This paper is based upon work that has been done for the Alloy Casting Institute at Battelle Memorial Institute. LIQUIDUS AND SOLIDUS TEMPERATURES OF HH AND HT TYPE ALLOYS Experimental Procedures Temperature-time curves were obtained during the cooling and solidification of several HH and HT type alloys. The metal was melted in an Ajax high-frequency induction furnace and poured into a coresand mold for cooling. The temperature measurements were obtained by means of a platinum, platinumrhodium thermocouple contained within a fused silica sheath, which was extended through the side wall of the dry core-sand mold to a point at about the center of the mold cavity, which was 3 in. in diameter by 5 in. deep. The cold junction of the thermocouple was kept in an ice bottle, and the temperature was recorded automatically on a direct-reading potentiometer recorder. Through a switching arrangement, the temperature recorded was checked occasionally with a portable Leeds and Northrup potentiometer indicator. Less than a 5°F. variation in the two instruments was always found. This is within the limit of accuracy of readings. The thermocouple used was checked for accuracy against a standard couple, both before use on this work and after completion of the work, by the instrument laboratory. Temperature-time Cooling Curves Fig. I is an enlarged reproduction of a part of one of the cooling curves over the temperature range of 2600° to 2200°F. for an alloy of the HT type with 0.45 per cent carbon, 16 per cent chromium, and 36 per cent nickel. This is a typically shaped cooling curve as obtained for the alloys. It will be noted that two temperatures are shown on Fig. r for the liquidus temperature. It is thought likely that the higher temperature, A, at the point at

Jan 1, 1945

By Kenneth Seaver

(San Francisco Meeting, September, 1915) INTRODUCTION IT is rather gratifying that in the field of the manufacture 'of refractories, in which, as a whole, foreign practice has surpassed us, the United States stands pre-eminent in the making of silica brick. In some instances European manufacturers have refused point-blank to credit the possibility of making to such specifications as are common with us, until the actual 'completed shapes were shipped for inspection. But both the manufacturer and consumer in foreign lands are now frankly learning from us, and benefiting by our advanced practice in this field, as is evidenced by the orders placed here and the efforts put forth abroad to come up to the standard of American-made material. In no metallurgical operation has the employment of silica brick spread with. such leaps and bounds as in the building of plants for the carbonization of coal, particularly in the byproduct coke oven. Today, in practically all types of oven, the structure above the floor level (except the facings) is of silica, while in the recuperative and in some regenerative types, its use is extended to that portion of the oven below the floor as well. By reason of the fact that there are a number of classes of refractories of higher silica content than the usual so-called fire-clay brick, there is sometimes a misunderstanding as to the class of material referred to as "silica" brick. We here refer only to a brick having a silica content of 94 per cent. or more and made usually from quartzite rock with a small percentage of lime as a binder. The term "silica" brick is sometimes rather loosely applied to brick front highly siliceous clays, or to a quartzite refractory of mingled fire-clay and quartz rock; but such products are not considered in this discussion.

Jan 9, 1915

By G. W. Healy

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By R. V. Higgins

This paper presents a computer method to obtain the shape factors and equal cell volumes of the channels for any well spacing pattern from a potentiometric model. By using this program the authors have processed the data for the seven-spot, direct line-drive and the staggered line-drive patterns. The data for the five-spot pattern had been previously processed by a noncomputer method and are included for completeness. The shape factors and volumes for the channels are presented in tables for those who want to use them to process data using their own permeability relationships and viscosities of their reservoir oils. The authors have used the data and sets of representative permeability curves to process sample calculationr of waterflood performances. The comparison of the calculated results shows that the influence of well spacing is small. The permeabilities of the reservoir rock to oil and water had a greater influence on oil recovery for a given pore-volume throughput of water than the well spacing pattern. The more water-wet the reservoir rock, the better the possibility of permeabilities which are conducive to good recovery. The viscosity of the reservoir oil also influences the recovery more than the well spacing pattern. The reduction in the percentage recovery of oil with increase in viscosity of the reservoir oils is small when oil viscosities are in the range of 0.1 to 3. Above this range the reductions in recoveries are extensive. Sample comparisons of the time required for different patterns to recover the oil are presented. Results of an example calculation are given to show the effect of the permeability profile on recovery. INTRODUCTION The effect of well spacing pattern on the recovery of oil when flooding with either gas or water has been studied by many investigators. Muskat et al.1 presented an analysis using conductivity, sweep efficiency and unit mobility to the time of breakthrough. Dyes et al.2 used experimental techniques (X-ray shadowgraphs) and different mobility ratios. They presented quantitatively the relationship between mobility and sweep efficiency at and after breakthrough. Hauber3 presented a method to predict waterflood performance for arbitrary well spacing patterns and mobility ratios. Craig et al.,4 using techniques similar to Dyes et al. to determine sweep efficiency for a five-spot pattern, added the use of relative permeability curves at breakthrough and thereafter. Douglas et al.5 sed rela- tive permeabilities and continuously changing saturations throughout the entire five-spot flood pattern. In obtaining their solutions they used finite-difierence equations. Hig-gins and Leighton6,7 also used relative permeabilities and continuously changing saturations throughout the pattern before and after breakthrough. They employed techniques that process a flood-pattern calculation on the computer in about one minute. The methods of Douglas et al. and Higgins and Leighton both checked closely the laboratory results for a wide range of mobility ratios. This paper presents some sample performances calculated by the Higgins and Leighton method that show the effect on recovery of different permeabilities and viscosities using the seven-spot, the line-drive and the staggered line-drive, as well as the fivespot flood pattern. No previous paper has presented these data using different permeability curves and continuously changing saturations throughout the flood patterns. The paper also presents (1) the results and analyses of the flood-pattern prediction, (2) the computer techniques for determining the shape factors and volumes from the potentiometric models for the foregoing flood patterns, and (3) the shape factors and volumes of the channels of the flood pattern in the event reservoir engineers may like to process waterflood calculations using their own permeability curves and reservoir oils. DESCRIPTION OF METHOD VOLUMES AND SHAPE FACTORS The use of channels taken from a potentiometric model (see Fig. 1) to aid in calculating the performances of water floods of nonlinear patterns has been thoroughly explained in the literature.0,7 Therefore, very little theory, discussion, or proof regarding this phase will be repeated in this paper. The computer method presented in this paper to calculate the volumes and the shape factors of the channels of potentiometric models employs the trapezoidal rule for the volumes and the Pythagorean theorem (the hypotenuse equals the square root of the sum of the squares of the two sides of a right triangle) for the shape factors. In calculating the volume of a channel, the area of each cell in the channel is determined and then multiplied by the thickness to obtain the volume. In determining the areas of the cells, trapezoids are constructed whose vertical sides are spaced Ax apart, as shown in Fig. 2. The length of the sides is the difference between an ordinate cut off by the top and bottom of the cell — usually equipo-tentials. The coordinates of the points along an equipo-tential or streamline are obtained by Lagrange's8 equation of interpolation for which the constants are coordinate points at the intersections. Three intersections for con-

Jan 1, 1965

By J. Charles Miller

THE expansion of facilities for rapid transportation of perishables by train, truck and airplane has necessitated consideration of refrigerants of a minimum weight and volume per pound of cooling and has stimulated the use of solid carbon dioxide commercially. The gas probably has not had wide application in the past in air-cooling equipment for mines, theaters or buildings, owing to its thermodynamic properties, as will be deduced from examination of Table 2. However, consumption of the liquid in carbonating beverages remains a dominant factor. In addition to these uses, carbon dioxide is employed to a limited degree as an explo-sive in the liquid form, as a freezing agent in plumbing, in laboratories for low-temperature work, and in the manufacture of golf balls.

Jan 1, 1936

By Peter F. Weiss

INTRODUCTION Austro-American Magnesite Co. of Radenthein, Carinthia, Austria, is a wholly owned subsidiary of General Refractories Company, Bala Cynwyd, USA, and has been incorporated since 1908. The raw material basis is the magnesite mine on Millstatt Alp, located in the mountains near Radenthein at an altitude of 1500 m above sea level. The mined crude magnesite is crushed in a surface crushing plant to minus 35 mm and consequently hauled to the processing plant in the valley by means of a cable conveyor of 7.5 km length. The annual production of 350,000 mt is accomplished with 20 supervisors and 122 workers (of those 60 are in the mine). The labor requirement for block caving is 0.2 man hr/mt, corresponding to an output of 40 mt/man/ shift. GEOLOGY The rock in this area mainly consists of crystalline type schist. There are mostly coarse crystalline garnet mica schists with varying mineral concentrations, and to a lesser degree, some deposits of amphibolite and marble. This petrographically rather homogeneous rock is divided into numerous different tectonic units (covers and scales). The magnesite deposit itself is a foreign body that also has been tectonically inserted. The ore body has a length of 600 m, is 450 m deep, and has a thickness of 60 m on average, varying substantially however, The contact with the accessory rock is very precise. The deposit 1 = ore body, 2 = previous open pit, 3 = caved in area, 4 = block under excavation, 5 = land slide consists of coarse crystalline magnesite in excess of 90 per cent. The few impurities consist of dolomite and talc. The lower part of the deposit is inclined parallel with the schists at approx. 40 degrees. In profile it can be seen, however, that the upper part of the deposit has been tilted over. This is a result of a post-glacial land slide reaching from the bottom of the valley at 1400 m above sea level to the peak of the mountain at 2100 m above sea level. Due to this land slide, with horizontal movements of up to 100 meters, as well as older tectonic events, the rock was crushed to a vast extent. Through mining, the land slide was reactivated; about 40 million cubic meters of rock slowly flow downhill almost like a plasticized mass. Near the surface, the rock is completely crushed and resembles a glacier rupture zone. This renders the originally impermeable rock completely water permeable so that practically all of the annual quantity of 1000 to 1100 mm of precipitation permeates the rock and flows down into the mine. The carbonate rock turns into the preferred aquifer. From 1700 to 2600 cubic meters of water have to be pumped from the mine daily. On one hand, additional problems are caused by the water in the mine, on the other hand we have learned to make use of the down- hill pressure forces to improve the crushing process during block caving. The boundary of the downhill shearing zone moves downward as mining goes deeper.

Jan 1, 1981

By Harold Roast

THE object of this investigation was to compare the arsenical antimony-lead alloy with some of the regular bearing-metal alloys. With this end in view, the following tests were made: 1. Chemical analyses to show the composition. 2. Thermal analyses. 3. Macroscopic examination of fractures. 4. Microscopic examination. 5. Tensile tests. 6. Crushing tests. 7. Scleroscope tests. 8. Brinell tests, at temperatures from 80° to 400° F. Tests 3 to 8 were conducted on both sand-cast and chill-cast specimens. For the purposes of this paper the alloys have been numbered from 1 to 6; their composition is as follows: LEAD, ANTIMONY, TIN, COPPER, ARSENIC, NUMBER PER CENT. PER CENT. PER CENT. PER CENT. PER CENT. 1 82.64 12.95 4.40 0.01 none 2 27.54 9.94 59.87 2.65 none 3 77.65 20.75 none 0.13 1.47 4 82.95 16.85 none 0.20 none 5 83.78 15.35 none 0.05 0.82 6 0.15 7.87 84.13 7.85 none The analysis, in the case of the antimony, was made by solution in sulfuric acid and titrated with permanganate. For tin, the ferric-chloride method was used; for copper, the alkaline separations, and the thiocyanate methods; for arsenic, volatilization of arsenic and titration with iodine. The lead, with the exception of alloy 6, was taken by difference.

Jan 2, 1922

By Fred D. DeVaney and

The coercimeter, as its name implies, is an instrument for measuring the coercive forcet of magnetic substances. It was developed by Davis and Hartenheim in the Special Studies Section, Metallurgical Division. A detailed description of this apparatus may be found elsewhere.2 The coercive force determinations of magnetic materials are interesting because of the relationship established by Gottschalk,4 who showed a linear relationship between the magnetization coercive force and the specific surface of comminuted particles. The value of this relationship in determining grinding efficiency has been shown by Dean.3 The determination of the surface contained in the subsieve sizes has always been a difficult problem for investigators. They made approximate measurements of the surface of coarse materials by sizing on screens, but for the determination of the surface of the sub-sieve sizes it was necessary to make detailed grain counts or elutriation tests, or to study dissolution rates. The technical literature contains many references to other methods for determining these surfaces, either by some special apparatus or by mathematical calculations based on distribution lines. Many of the methods are long and tedious, and the results of some, at least, are questionable. he turbidimeter gives quick results on ground cement. By using magnetite as the material to be ground, a simple determination of its coercive force by the coercimeter, requiring 10 minutes or less, can be transposed directly and accurately into units of relative surface. This subject has been pursued further by the U. S. Bureau of Mines in cooperation with the Missouri School of Mines and Metallurgy, Rolla, Mo., and the following is a description of the results.

Jan 1, 1939

By Fred D. DeVaney and

The coercimeter, as its name implies, is an instrument for measuring the coercive forcet of magnetic substances. It was developed by Davis and Hartenheim in the Special Studies Section, Metallurgical Division. A detailed description of this apparatus may be found elsewhere.2 The coercive force determinations of magnetic materials are interesting because of the relationship established by Gottschalk,4 who showed a linear relationship between the magnetization coercive force and the specific surface of comminuted particles. The value of this relationship in determining grinding efficiency has been shown by Dean.3 The determination of the surface contained in the subsieve sizes has always been a difficult problem for investigators. They made approximate measurements of the surface of coarse materials by sizing on screens, but for the determination of the surface of the sub-sieve sizes it was necessary to make detailed grain counts or elutriation tests, or to study dissolution rates. The technical literature contains many references to other methods for determining these surfaces, either by some special apparatus or by mathematical calculations based on distribution lines. Many of the methods are long and tedious, and the results of some, at least, are questionable. he turbidimeter gives quick results on ground cement. By using magnetite as the material to be ground, a simple determination of its coercive force by the coercimeter, requiring 10 minutes or less, can be transposed directly and accurately into units of relative surface. This subject has been pursued further by the U. S. Bureau of Mines in cooperation with the Missouri School of Mines and Metallurgy, Rolla, Mo., and the following is a description of the results.

Jan 1, 1939

By Lincoln F. Elkins, John T. Cooke

Injection of gas to increase oil recovery has been considered for almost all important discoveries during the past ten or fifteen years. However, the number of gas injection projects having sufficient history and data is too limited to permit valid generalities of effectiveness of gas injection. Management and engineers are faced with a difficult problem of selecting those reservoirs which are susceptible to profitable application of gas injection. Injection of gas to maintain high pressure favors some factors affecting reservoir performance such as viscosity, surface tension, and formation volume factor of oil by keeping gas in solution and favors some operating features such as extending flowing life of wells and storing part of the produced gas for future use or sales. Injection of gas at low pressure involves lower compression ratio, or at least a single gas-gathering system, larger displacement volume in the reservoir per unit of gas handled, and permits effective utilization of the naturally existing energy and agent for oil displacement that is gas dissolved in oil. Each program is thus a compromise to meet optimum economic conditions while striving to attain maximum recovery of this important nautral resource. The statement has often been made that pressure maintenance would greatly increase oil recovery by permitting abandonment of formation oil inflated with gas in solution rather than abandonment of the same liquid volume of tank oil, if the same terminal oil saturation could be attained. Simple calculations indicate increases in oil recov- ery as high as one hundred per cent on this basis for high formation volume factor oil encountered in current deep drilling. Important in this statement is "if the same terminal oil saturation could be attained." Implicit in this statement are the requirement of physical

Jan 1, 1949

By John T. Cooke, Lincoln F. Elkins

Injection of gas to increase oil recovery has been considered for almost all important discoveries during the past ten or fifteen years. However, the number of gas injection projects having sufficient history and data is too limited to permit valid generalities of effectiveness of gas injection. Management and engineers are faced with a difficult problem of selecting those reservoirs which are susceptible to profitable application of gas injection. Injection of gas to maintain high pressure favors some factors affecting reservoir performance such as viscosity, surface tension, and formation volume factor of oil by keeping gas in solution and favors some operating features such as extending flowing life of wells and storing part of the produced gas for future use or sales. Injection of gas at low pressure involves lower compression ratio, or at least a single gas-gathering system, larger displacement volume in the reservoir per unit of gas handled, and permits effective utilization of the naturally existing energy and agent for oil displacement that is gas dissolved in oil. Each program is thus a compromise to meet optimum economic conditions while striving to attain maximum recovery of this important nautral resource. The statement has often been made that pressure maintenance would greatly increase oil recovery by permitting abandonment of formation oil inflated with gas in solution rather than abandonment of the same liquid volume of tank oil, if the same terminal oil saturation could be attained. Simple calculations indicate increases in oil recov- ery as high as one hundred per cent on this basis for high formation volume factor oil encountered in current deep drilling. Important in this statement is "if the same terminal oil saturation could be attained." Implicit in this statement are the requirement of physical

Jan 1, 1949

By C. S. Smith, E. W. Palmer

For several years an investigation has been in progress in the research laboratory of The American Brass Co. to determine the thermal and electrical conductivities of most copper alloys of commercial importance and several of scientific interest. This paper contains such data on the binary alloys of copper with silicon, aluminum, manganese and nickel, and on a large number of ternary or more complex alloys. Some interesting general relationships between the thermal and electrical conductivities for all copper alloys at all temperatures are pointed out. The data for the copper-zinc, copper-phosphorus and copper-tin binary systems have already been published1,2 † except for the electrical conductivity at 200" C., which is given in the appendix of this paper. Literature on Thermal Conductivity of Copper Alloys The papers referred to above contained a summary of the figures available in 1929 for the thermal conductivity of copper alloys. There is given in Table 1 herewith a selection of the data that have appeared since that time. The measurements of Hanson and Rogers3 are particularly interesting since they cover a series of alloys in the alpha solid solution range and show the effect of heat-treatment. Their alloys were tested as annealed castings, and are not therefore directly comparable to the worked alloys measured in the present investigation, although the difference is small. Bailey's determinations4 were carried out on the alloys used by Lees6 in 1906, and extend his results to higher temperatures. It is most unfortunate that the alloys were not analyzed, for the approximate compositions given are hardly sufficient identification of the material. It is equally to be regretted that neither Hanson and Rogers nor Bailey give data for the electrical conductivities of their samples. Sager6, using the heat-wave method of King, determined the thermal conductivity of copper, nickel and four alloys of the two metals. His results are included in Table 1.

Jan 1, 1935

By C. S. Smith, E. W. Palmer

For several years an investigation has been in progress in the research laboratory of The American Brass Co. to determine the thermal and electrical conductivities of most copper alloys of commercial importance and several of scientific interest. This paper contains such data on the binary alloys of copper with silicon, aluminum, manganese and nickel, and on a large number of ternary or more complex alloys. Some interesting general relationships between the thermal and electrical conductivities for all copper alloys at all temperatures are pointed out. The data for the copper-zinc, copper-phosphorus and copper-tin binary systems have already been published1,2 † except for the electrical conductivity at 200" C., which is given in the appendix of this paper. Literature on Thermal Conductivity of Copper Alloys The papers referred to above contained a summary of the figures available in 1929 for the thermal conductivity of copper alloys. There is given in Table 1 herewith a selection of the data that have appeared since that time. The measurements of Hanson and Rogers3 are particularly interesting since they cover a series of alloys in the alpha solid solution range and show the effect of heat-treatment. Their alloys were tested as annealed castings, and are not therefore directly comparable to the worked alloys measured in the present investigation, although the difference is small. Bailey's determinations4 were carried out on the alloys used by Lees6 in 1906, and extend his results to higher temperatures. It is most unfortunate that the alloys were not analyzed, for the approximate compositions given are hardly sufficient identification of the material. It is equally to be regretted that neither Hanson and Rogers nor Bailey give data for the electrical conductivities of their samples. Sager6, using the heat-wave method of King, determined the thermal conductivity of copper, nickel and four alloys of the two metals. His results are included in Table 1.

Jan 1, 1935

By G. S. Cole, G. F. Bolling

ThIS note accompanies a study of grain structure changes in metal ingots produced by the alteration of fluid motion.1 Although the Prandtl Number of aqueous solutions is much higher than that for metals, it is quite instructive to see the simulation of freezing, as pointed out by Jackson and coworkers.2-4 Accordingly we have observed the effects of natural thermal convection, the changes induced by a steady-state rotation in one direction, and the changes under oscillation.' Temperature measurements were made under duplicate conditions whenever the visual observations appeared interesting. A solution of 15 pct NH4C1 in water was chosen. In each case the solution was preheated to 90°C in a 4-in.-diam Pyrex beaker filled to a level of about 5-in. depth and covered to prevent convective air cooling. The beaker was then placed in a container of iced brine, suitably arranged on a rotating table for movement about its cylindrical axis. Upon immersion in the brine under static conditions, fluid flow was observed near the wall of the beaker before the onset of crystallization, which generally commenced only after the temperature fell to 51.5"C. The region of flow extended about 1 mm from the wall and could not be observed elsewhere. The measured radial temperature increased sharply within 1 cm from the wall and thus over a distance considerably greater than that observed for the flow. However, we note that this difference of approximately one order of magnitude between hydrodynamic and thermal boundary layers should be expected for aqueous solutions, in contrast to metallic liquids. Beyond this layer the temperature was isothermal at a given height and in general nearly 10°C warmer than at the wall. The overall visual observation was therefore supported quite well by temperature measurement. There was also a vertical temperature gradient of nearly 2°C per cm throughout the liquid increasing from the colder bottom; this of course could not be observed visually. Eventually crystals precipitated from solution. (It

Jan 1, 1968

By H. I. Aaronson

ONLY limited studies have been made of pro-eutectoid a morphology in hypoeutectoid Ti-Cr alloys during previous investigations, 1-3 The nature of the eutectoid reaction, ß?a + TiCr2, has been considered in somewhat more detail.1,2,4,4 Inasmuch as the proeutectoid ferrite reaction in plain carbon steels has recently been extensively investigated in this laboratory, advantage has been taken of the opportunity to compare the morphologies developed in two rather different eutectoid systems in order to permit a preliminary estimate to be made of the degree of generality which may be ascribed to the various results obtained. Experimental Procedure The chemical analyses of the alloys used are given in Table I. The 7.22 pct Cr alloy was prepared by the Battelle Memorial Institute from iodide titanium and high purity chromium. The initial ingot was made by arc melting a master alloy and iodide titanium. The resultant ingot was twice remelted. by the consumable electrode technique. Upset forging at 950°C reduced the final ingot to 3/4 in. sq bars. The 10.94 pct Cr alloy was prepared by the Titanium Metals Corp. of America from sponge titanium and chromium of ordinary purity. This alloy was melted twice by the consumable electrode technique, forged at 1200° to a 3/4 in. sq bar, and rolled at 815°C to a 1/2 in. round. Specimens 1/4 in. x 1/4 in. x 1/16 in. were cut from the 7.22 pct Cr alloy; halves of disks 1/2 in. in dlam and 1/16 in. thick served as specimens of the 10.94 pct Cr alloy. These specimens were individually encapsulated in Vycor, Each capsule was evacuated three times to a pressure of 2 to 6 x lo-' mm Hg and flushed twice with a reduced pressure of argon prior to sealing. The inclusion of two small packets of zirconium chips permitted the capsules to be outgassed and internally gettered, without heating the specimen, prior to heat treatment. The specimens were solution annealed for 40 min at 1000°C, isothermally reacted in deoxidized lead pots, and quenched in iced water. Most of the isothermal reaction treatments were carried out at 25" intervals between 725° and 550°C on specimens of the 7.22 pct Cr alloy and at 650°C on specimens of the 10.94 pct Cr alloy. Results and Discussion Morphologies of Proeutectoid a*—Kinetics of the ß?a Reaction: Fig. 1 shows the TTT-curves for the beginning of the proeutectoid a and the eutectoid reactions in the temperature range investigated in the 7.22 pct Cr alloy. The M, temperature in this alloy is below 0°C. The curve for the beginning of the proeutectoid a reaction is in good agreement with that of Frost, Parris, Hirsch, Doig, and Schwartz' for a 7.54 pct Cr alloy, appears at considerably earlier reaction times than the corresponding curve presented by Rostoker4 for a 7 pct Cr alloy, and lies athwart the curve of Spachner and co-workers11 for an 8 pct Cr alloy. Differences in criteria for the beginning of the a reaction and the relatively high rate of this reaction at lower temperatures presumably account for some of these divergences and may also explain, in part, the apparent failure of an iodide-base 7.22 pct Cr alloy to react more slowly than sponge-base 7 to 8 pct Cr alloys. Grain Boundary Allotriomorphs: Crystals of this morphology nucleate at and grow preferentially and more or less smoothly along the matrix grain boundaries.5-7 Allotriomorphs are the first morphology to precipitate at most grain boundaries at reaction temperatures from 725°C, the highest temperature studied, at least through 575°C. Fig. 2 Shows typical allotriomorphs, formed during an early stage of transformation at 725°C. Grain boundary allotriomorphs are not the predc=iaant morphology at late reaction times at any temperature studied. However; from 725" through

Jan 1, 1958

By Thomas L. Garrard, James A. Sprague, Rex B. McLellan, Samuel J. Horowitz

A simple rnodel for interstitial solid solutions has been devised in which each solute atom interacts with the solzlent lattice in such a way as to exclude an integral number of nearest-neighbor sites from being occupied by solute atoms. The vemaining interstitial sites ave not affected. In calculating the entropy of such a solution the increase in the number of interstitial sites available to solute atoms due to the ozlerlap of blocked sites is taken into account. The ther-modynamic functions and the solute activity fov the solution rnodel are calculated. It is shown that considevation of the overlap sues vise to a correction term of the order 8' ( where 0 is the ratio of solute to solvent atoms) in the thevmodynamic functions of the solution and the solute activity. The theo,uetical equation for the solute activity was used to analyze the available data for the activity of carbon in austenite at three different temperatures. The use of a computer enabled many comparisons to be made between the experimental activity data and those predicted by both the complex blocking model and the simple, widely used blocking model in which the ozierlapping of blocked sites is not taken into consideration. Even though at the highest concentvations oj carbon the value of 0 is small it is shown that the best fit to the experimental data is found with the complex blocking model. RECENTLY it has been shown by analysis of gas-solid equilibriums that many interstitial solid solutions can be described by the quasi-regular solution model in which the partial energy of solution E, is independent of composition and, apart from a composition-independent term due to nonconfigurational factors, the partial entropy is that of an ideal solution. Dilute solutions of nitrogen in both bcc and fcc iron,' dilute solutions of oxygen and silver,' carbon in a Fe,' and dilute solutions of carbon in ? Fe2 are all quasi-regular. In addition many hydrogen-metal solutions, both dilute and concentrated (with the notable exceptions of the H-Ni and H-Pd systems), can be described by this model.3 However, it has been shown that, at various temperatures, solutions of carbon in ? Fe begin to depart strongly from quasi-regular behavior at low concentrations. A plot of the activity of carbon in ? Fe relative to pure graphite vs atom fraction of carbon (Cc) calculated from Smith's data4 begins to depart from the (nonlinear) plot for a quasi-regular solution at about Cc = 0.02. Several statistical models have been proposed to account for the thermodynamic behavior of carbon in y Fe. Darken and smith4 set up a model in which a carbon atom in its octahedral site in the fcc lattice has either one or no neighboring carbon atoms in the twelve nearest-neighbor octahedral sites. It is assumed that the number of carbon atoms having more than one nearest neighbor is negligibly small and that a solute atom does not interact with another solute atom located at a greater distance than the first shell of interstitial sites. Thus this model contains two characteristic interaction energies. Darken and Smith showed that this model gives reasonable agreement with the measured variation of carbon activity ac with composition. It is noteworthy that Darken and Smith concluded from their analysis of the activity data using this model that there was a repulsive force between carbon atoms in austenite which reduces the concentration of C-C pairs below that corresponding to random mixing. Recently Aaronson, Domian, and pound5 have considered in detail the statistical model developed by Lachere and by Fowler and Guggenheim7 and have shown that it is compatible with the activity data for carbon in austenite. In Darken's model the energy of solution of carbon in austenite is dependent on temperature and concentration; the departure from Henry's law arises from the concentration dependence of the energy of solution. In Aaronson, Domian, and Pound's discussion of the Lacher, Fowler, Guggenheim model the interaction energy wy between adjacent carbon atoms in austenite is strongly temperature-dependent. Aaronson et al . suggested that this temperature dependence of wy and hence the energy of solution of carbon could be explained either by the formation of clusters of carbon atoms (despite the repulsive nature of wy) or by the dual occupancy of the octahedral and tetrahedral sites by the carbon atoms. However, a temperature-dependent heat of solution

Jan 1, 1968

By B. H. Caudle, M. D. Witte

In predicting the performance of a pattern injection operation, the engineer needs to know both the amount of oil to be recovered and the rate at which the recovcry will take place. This paper- describes fluid flow model studies on the effect of mobility ratio on the rate of oil recovery in a five-spot. The results show the change in fluid conductivity (total flow rate/pressure drop) as the sweep-ont pattern increases for mobility ratios between 0.1 (and 10. There data, when cornbitted with a knowledge of reservoir permeabilities and sweep-orit pattern efficiencies, cata he used to predict the cLrmulntivr oil production as a function of time for homogeneous five-spot injection systems. INTRODUCTION The flow potential in a pattern flood element is a function of the mobility ratio and how far the injected flood front has gone.1,2 For a waterflood project having a mobility ratio of one, the conductance—which is the flow rate per unit pressure drop (q/Ap)—-will remain the same throughout the life of the flood. If the mobility ratio is favorable ( < I), the conductance of the project will drop continuously throughout the operation. If, on the other hand, the mobility ratio is unfavorahlc. the conductance ratio will increase continuously. Therefore, if the reservoir engineer wishes to predict either the rate at a specified pressure or the pressure at some rate for a secondary recovery project, he must know how the conductance will vary during the flood. Other investigators have studied this problem using potentiometric models&apos; or analytical solution&apos;. The

By Haakon Styri

In discussion of Dr. Fitterer&apos;s paper on electrolytic separation of slag inclusions, some results from experiments on electrolyzing high-carbon steels at the SKF Research Laboratory were given. l We had been working for a number of years on chemical methods of separating the inclusions but could not find any solvent that would dissolve the steel without attacking some of the inclusions, particularly the sulfides in which we were mostly interested at the time, nor any that would dissolve all sulfide or silica in filings as fine as 300 mesh without attacking the iron. Electrolytic methods had also been tried without any real progress until we learned from the Bureau of Mines about the use of the collodion membrane around the anode. Our early difficulties were to some extent different from those of the Bureau of Mines, perhaps because of experimenting on steels of higher carbon content, but most of our difficulties were of the same nature as those of the Bureau. Formation of large quantities of basic hydroxides was traced to the use of impure and oxidized ferrous sulfate. To protect from oxidation from the atmosphere during electrolysis, after purer chemicals were obtained, a thin layer, 54 in. or less, of molten paraffin was poured over the surface of the cathode liquid, where it solidified. It was found desirable also to hold the cathode chamber slightly acid by initial addition of 0.1 per cent acid (sulfuric or hydrochloric) to prevent precipitation of the hydroxide. This acidity would decrease gradually and the cathode chamber would become neutral before the end of the electrolyzing. The increase in acidity in the anode chamber during our early experiments had appeared to cause attack of the precipitated sulfides in the residue, which originally was analyzed by volumetric method for sulfur, and for this reason a 10 per cent sodium citrate solution was substituted for the sulfate in the anode chamber. With the use of the more reliable Eschka method for sulfur determination (as in coke), there was however no serious attack on the sulfides in the anode chamber with a variety of different liquids, as shown in Tables 2 and 4. The Eschka method gives a higher sulfur value than

Jan 1, 1933

By W. C. Knopf, I. M. LeBaron

In the Carlsbad area potash is dry-mined and wet-concentrated. Wet concentration involves recircu-lation of saturated brines, with resultant difficulties of brine disposal and inherent losses in recovery through solution of the KCl. A dry beneficiation process for potash minerals would offer many advantages over present methods. International Minerals & Chemical Corp. has been working on development of a dry process for some time. This article is a progress report. Potash ores available in this country are largely mixtures of halite and sylvite contaminated with slimes and often with many sulfate and magnesium minerals. Electrostatic concentration of KCl when the contaminating minerals are in low percentage has been accomplished. Continuous production of better than 60 pct K2O concentrate from high potassium sulfate ores has not been demonstrated at the present time. Laboratory Procedure: Laboratory work on electrostatic beneficiation of potash minerals has been carried out using both pure crystals and mined ore. Electrostatic separation of the two main components of potash ore, sylvite (KCl) and halite (NaCl), is accomplished by first heat-treating the ore to allow for electric charging of the particles. Preferential exchange of&apos; electrical charges between different mineral particles through surface contact is the principal mechanism involved. After proper conditioning of the particle surfaces, the oppositely charged minerals are dropped vertically into a horizontal electric field having a field gradient from about 5000 to 15,000 v per in. The particles are free-falling in the field. A suitable power supply is used to produce the proper total voltage for the electric field. Total required voltage is, of course, a function of electrode spacing. A typical electrode arrangement with power supply is shown in Fig. 1. In general, the total voltage on any system is 75,000 to 90,000 v. Power consumption is negligible, as leakage at insulators and corona discharge are the main losses in the system. Optimum preheat temperatures for pure material components generally are not the same as for mined minerals. Fig. 2 shows clearly that maximum recovery on a 50 pct pure KCl, 50 pct pure NaCl mixture occurs at a preheat temperature of about 600°F. In this test the preheat mixture was allowed to cool to about 225°F before dropping through the electric field. The optimum temperature for sep- aration is practically never the optimum temperature of preheat. Optimum separation for mined Carlsbad potash ores occurs when a preheat temperature closer to 900°F is used, as shown by Fig. 3, which plots percent sylvite (KCl) in the concentrate and tails as a function of preheat temperatures. Here again the ore was allowed to cool to about 225°F before separation. It should be noted that efficiency of separation increases continuously with increasing preheat temperatures until incipient fusion of the ore takes place at about 950°F. The increase in optimum preheat temperature for Carlsbad ores over the pure minerals can be traced to the effect of the clay slimes intimately associated with the mined potash. If the slimes associated with the ore are removed by washing with alcohol or other non-aqueous material, the necessity of preheating to the high temperature is removed. This temperature range has been proved critical within these limits during continuous pilot plant operation. Concentrate and tailings grade and optimum recovery also are functions of the temperature of the potash mineral particles during separation in the electric field. Fig. 4 presents data indicating that feed to the rougher pass should range between 150°F and 275°F for best results. It has been found by subsequent pilot plant work that these temperatures can be maintained in actual operation.

Jan 1, 1959