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By S. Mellgren, W. Opie

AN equilibrium state of importance in the process of electrolytically depositing titanium from fused chloride electrolytes is that which exists between titanium metal, titanium dichloride, and titanium trichloride. This can be expressed by the reaction titanium concentration of the solution, temperature, and the proportion of strontium chloride and sodium chloride in the solution. Procedure The general procedure used consisted of the following steps: 1) Development of an analytical method for determining Ti+2 and total titanium. 2) Preparation of batches of fused salt solutions containing various amounts of total titanium, Ti+2 and Ti+3 3) Blending of the prepared batches and excess titanium metal in Vycor tubes and allowing the solutions to come to equilibrium. By blending, solutions with different total titanium content could be prepared and equilibrium could be approached from the high Ti+2 and low Ti+2 sides. 4) Studying the effect of titanium concentration, temperature, and the mole ratio of the solvent chlorides, SrC1, and NaC1, upon the equilibrium.

Jan 1, 1958

By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing' for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing's correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine's multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

As reported in Drift last month demolition of old buildings on the 47th St. site has been completed, and detailed plans and studies for the new structure are well underway. As this issue was being sent to press the $5 million industry- business phase of the fund campaign had passed the half- way mark toward its goal. Target date for the building program is 1960.

Jan 5, 1958

By C. C. Furnas, S. P. Kinney

The efficient operation of a blast furnace depends primarily upon efficient contact between the descending streail1 of solid materials and the ascending stream of gas. A program of research dealing with the interior of the present-day furnace is being carried by the U. S. Bureau of Mines along two lines: (I) observations on commercial furnaces and (2) experiments in the laboratory. Through the courtesy of the officials of the Illinois Steel Co. it was possible to make a detailed investigation of the interior of the shaft of NO. 4 furnace at the company's South Works, South Chicago, Ill. The experimental work is reported in a IT. S. Bureau of Mines bulletin' which will include the results of several thousand observations on the interior of the shaft of this furnace. Such of the data as are presented later in this paper constitute only a brief summary. The second part of the work has been conducted in the laboratory. Only one phase of the laboratory investigation has been completed at the present time, namely, the flow of gases through beds of broken solids." The object of this papcr is to correlate the results of the two different lines of research and to present a. more or less complete picture of the condition of the interior of a blast furnace by giving approximate, quantitative data of the actual size-distribution of solid particles in a typical furnncc, and of the efficiency of contact between the gas and solid phases. With such data before him the operator or the experimenter not only has a much better idea of the actunl conditions inside a furnace, hut he also knows in what direction to look for possible improvement. The discussion which follows presents only a few of the items studied and reported; those persons who are particularly interested in all the result's of this investigation must refer to the aforementioned publication.

Jan 1, 1929

By D. B. Williams

For the first time in the history of the Venezuelan petroleum industry production exceeded 200 million barrels. The total production for all fields amounted to 205,430,869 bbl., which is more than 9 per cent of the world's 1939 total. This is an increase of over 15 million barrels or 8.0 per cent above the 1938 figure, which, compared with the slightly less than 2 per cent increase of the 1938 figure over 1937, shows the marked activity in Venezuela during the past year. The Maracaibo Lake fields are still the predominating factor in Venezuelan production, showing an increase of approximately 9½ million barrels over last year's figure and accounting for 71.8 per cent of Venezuela's total. Lagunillas continues to hold precedence as a single field, having yielded 47.1 per cent of the accumulative total and 39.4 per cent of 1939's total. This field showed an increase of slightly more than 3½ million barrels over 1938. Tia Juana, the second largest field, attained a record production, increasing its percentage of the Venezuelan total from 23.4 in 1938 to 23.7 in 1939. The La Rosa field, which includes Punta Benitez and Ambrosio, declined from 13.7 to 12.0 per cent; Bachaquero, the southernmost Lake field, which came into regular production at the end of 1938, contributed over 31/3 million barrels. Quiriquire, in eastern Venezuela, ousted La Rosa as the third largest producing field, and, although production increased by 11/3 milliorl barrels, percentage of the total declined from 13.2 to 12.9. Mene Grande, the oldest field, declined from 6.6 per cent in 1938 to 5.9 in 1939. Tem-blador produced for a whole year for the first time and yielded 3,647,867 bbl. The Colon district, in the Maracaibo Lake area, comprising the Tarra-Los Manueles fields, showed slight increases, as also did Cumarebo and Pedernales. Construction of the 16-in. pipe line from Oficina to Puerto La Cruz (Guanta), the longest line of this size in the world, was completed toward the end of the year and this new field in eastern Venezuela started shipping oil in December. This field is operated by the Mene Grande Oil Co. and was credited with a production of 2,347,625 bbl. in 1939. Jusepin field, some 25 miles southwest of Quiriquire in eastern Venezuela,

Jan 1, 1940

By D. B. Williams

For the first time in the history of the Venezuelan petroleum industry production exceeded 200 million barrels. The total production for all fields amounted to 205,430,869 bbl., which is more than 9 per cent of the world's 1939 total. This is an increase of over 15 million barrels or 8.0 per cent above the 1938 figure, which, compared with the slightly less than 2 per cent increase of the 1938 figure over 1937, shows the marked activity in Venezuela during the past year. The Maracaibo Lake fields are still the predominating factor in Venezuelan production, showing an increase of approximately 9½ million barrels over last year's figure and accounting for 71.8 per cent of Venezuela's total. Lagunillas continues to hold precedence as a single field, having yielded 47.1 per cent of the accumulative total and 39.4 per cent of 1939's total. This field showed an increase of slightly more than 3½ million barrels over 1938. Tia Juana, the second largest field, attained a record production, increasing its percentage of the Venezuelan total from 23.4 in 1938 to 23.7 in 1939. The La Rosa field, which includes Punta Benitez and Ambrosio, declined from 13.7 to 12.0 per cent; Bachaquero, the southernmost Lake field, which came into regular production at the end of 1938, contributed over 31/3 million barrels. Quiriquire, in eastern Venezuela, ousted La Rosa as the third largest producing field, and, although production increased by 11/3 milliorl barrels, percentage of the total declined from 13.2 to 12.9. Mene Grande, the oldest field, declined from 6.6 per cent in 1938 to 5.9 in 1939. Tem-blador produced for a whole year for the first time and yielded 3,647,867 bbl. The Colon district, in the Maracaibo Lake area, comprising the Tarra-Los Manueles fields, showed slight increases, as also did Cumarebo and Pedernales. Construction of the 16-in. pipe line from Oficina to Puerto La Cruz (Guanta), the longest line of this size in the world, was completed toward the end of the year and this new field in eastern Venezuela started shipping oil in December. This field is operated by the Mene Grande Oil Co. and was credited with a production of 2,347,625 bbl. in 1939. Jusepin field, some 25 miles southwest of Quiriquire in eastern Venezuela,

Jan 1, 1940

By R. B. Adair, J. S. Browning

The laboratory batch and continuous flotation pilot plant tests demonstrated the technical feasibility of recovering high grade mica concentrates from weathered mica pegmatite ores of Alabama and Georgia. The research indicated that combinations of anionic and cationic collectors may be used effectively for flotation of fine size mica from weathered pegmatite ores. In continuous tests, concentrates containing 98.5% mica were obtained from the Georgia pegmatite ore; the Alabama pegmatite ore concentrates contained 98.4% mica. The recoveries were 91 and 89% respectively. INTRODUCTION The principal uses of fine ground mica are as a filler in wallboard joint cement, as a filler and surface coating for roofing, as an ingredient in paints, and in oil well drilling mud. The mineral has other uses in the manufacture of rubber, wallpaper, plastics, welding rods, electric insulation, house insulation, and textiles, and as an annealing agent in metal treatment. In recent years, more than 99% of the domestic mica produced has been scrap and flake mica (mica which does not meet specifications for sheet mica and is used for producing fine ground mica). There has been a continued increase in mica production for several years, the 1963 production of scrap and flake mica totaling 117,251 tons.1 Ground mica is obtained primarily by crushing and milling pegmatites and schists. To a lesser extent, mica is produced as a byproduct of kaolin washing and feldspar and spodumene flotation operations. The processes used in recovering mica by crushing and milling pegmatites are generally simple, consisting of various combinations of alternate roll crushers and trommel screens that separate the mica and gangue at screen sizes coarser than 6-mesh. As these processes are designed to recover only coarse mica, high losses in the plant rejects are common. Large tonnages of tailings from the crushing and screening plants have been accumulated in a number of areas. Methods for treating such products were developed by the Bureau of Mines in 1941,2 but have not been generally applied. More recently, mica flotation research has been completed and published by the Bureau of Mines.3 These methods required complete removal of 150- to 200-mesh materials from the flotation feed with consequent fine mica losses. Later, the Bureau of. Mines investigated methods for-recovering fine size mica from pegmatite ores after desliming sufficiently to remove clay materials, but not so drastically as to remove the fine sands. This report summarizes the results of these studies. The process developed was effective on pegmatite ores from two locations and should be applicable to the commercial treatment of other mica-bearing pegmatite ores and fine rejects that have been accumulated at various mica-milling operations. DESCRIPTION OF ORES The ores used in the investigation were obtained from the Dixie Mines, Inc., Heflin, Alabama, and the Ruberoid Corporation, Hartwell, Georgia. The sample from Alabama contained muscovite and quartz, with a high percentage of clay, and minor amounts of biotite, kaolin, limonite and tourmaline. The mica in the ore was essentially all minus 4-mesh in size and was free of attached mineral grains. The Georgia sample contained muscovite and quartz, with minor amounts of biotite, kaolin, and limonite. The mica in the ore, which was essentially all minus 4-mesh, was liberated. Petrographic analyses of the two samples are given in Table I. THE ANIONIC-CATIONIC MICA FLOTATION METHOD Previous investigators2,3 have reported that complete desliming of mica ores at 150- to 200-mesh was required prior to flotation with cationic collectors to obtain satisfactory selective separation of the mica from the other mineral components. Numerous tests were made at the Tuscaloosa Metallurgy Research Center to determine if some reagent combination could be used to selectively float finer size mica without complete desliming. The investigation led to development of a process using a simple reagent com-

Jan 1, 1967

By C. E. Lesher

Low-temPeRatUre carbonization needs no introduction to the literature on coal. This paper will attempt no review of that literature; it tells the story of the commercial development of one of the processes for carbonizing coal at so-called low temperatures, dealing with the technology and economics of the process rather than with the design of equipment. The process used is that covered by the patents of C. B. Wisner, with improvements and changes made by the Pittsburgh Coal Carbonization Co. The important and novel feature of the process is the phenomenon of making the product in ball form (Fig. 1). Melting coal dust into smokeless solid fuel in an apparatus as simple as a revolving cylinder of ordinary mild steel has been proved to be practical. Furthermore, it has been found that the process has a wide application, for by applying a knowledge of why and how this balling action is accomplished, the apparatus can be designed and adapted to treat any coal that has a certain minimum agglutinating property. The operating plant is 20 miles west of Pittsburgh, adjacent to the Champion preparation plant of the Pittsburgh Coal Co. The coal used is cleaned minus ?-in. or finer sizes. The products are low-tem-perature coke, tar and tar products. Present capacity is 7000 tons per month of low-temperature coke and 140,000 gal. of tar. There is no surplus gas for sale, and none of the light oils are stripped from the gas. The coke is marketed in two sizes, 1 to 2 in. and 1 to 6 in., through retail coal dealers for domestic consumption in hand-fired furnaces, and for fireplace fuel. The smaller size is bagged by dealers. Crude tar and many distillates and road tars are sold. Acknowledgments During the 10 years in which the work that is summarized in this paper has been under way, many have contributed time and effort, faithful service and fruitful thinking. Whatever success has attended

Jan 1, 1940

By C. E. Lesher

Low-temPeRatUre carbonization needs no introduction to the literature on coal. This paper will attempt no review of that literature; it tells the story of the commercial development of one of the processes for carbonizing coal at so-called low temperatures, dealing with the technology and economics of the process rather than with the design of equipment. The process used is that covered by the patents of C. B. Wisner, with improvements and changes made by the Pittsburgh Coal Carbonization Co. The important and novel feature of the process is the phenomenon of making the product in ball form (Fig. 1). Melting coal dust into smokeless solid fuel in an apparatus as simple as a revolving cylinder of ordinary mild steel has been proved to be practical. Furthermore, it has been found that the process has a wide application, for by applying a knowledge of why and how this balling action is accomplished, the apparatus can be designed and adapted to treat any coal that has a certain minimum agglutinating property. The operating plant is 20 miles west of Pittsburgh, adjacent to the Champion preparation plant of the Pittsburgh Coal Co. The coal used is cleaned minus ?-in. or finer sizes. The products are low-tem-perature coke, tar and tar products. Present capacity is 7000 tons per month of low-temperature coke and 140,000 gal. of tar. There is no surplus gas for sale, and none of the light oils are stripped from the gas. The coke is marketed in two sizes, 1 to 2 in. and 1 to 6 in., through retail coal dealers for domestic consumption in hand-fired furnaces, and for fireplace fuel. The smaller size is bagged by dealers. Crude tar and many distillates and road tars are sold. Acknowledgments During the 10 years in which the work that is summarized in this paper has been under way, many have contributed time and effort, faithful service and fruitful thinking. Whatever success has attended

Jan 1, 1940

By P. Greenfield, P. A. Beck

The phase is a hard and extremely brittle material with a tetragonal crystal structure, containing 30 atoms per unit cell' It occurs in many binary and ternary alloys of the transition elements. The existence of twelve a phases has been reported in binary alloys of metals from the group vanadium, chromium, molybdenum, and tungsten with metals from the group manganese, iron, cobalt, and nickel. It is a characteristic fact that the composition of the o- phases in the various binary systems is not the same. Rather, there is a gradual shift in composition, for instance in the series of chromium a phases, approximately as follows: CrMn,, FeCr, Cr3Co,. In recent years several ideas have been put forward to account for this variability of composition. SullyZ proposed that a was a type of electron compound, characterized by 1.7 electrons per atom in excess of the number required to fill the Pauling atomic orbitals. These excess electrons were supposed to just fill the first Brillouin zone of the u structure. However, later work indicated that the phase is ferromagnetic at low temperatures, so that a- is unlikely to be a full zone compound.~ Another proposal,* which is also based on the structure of the transition elements advanced by Pauling, and in fact leads to essentially the same a compositions as Sully's theory, suggests that the u phase is characterized by a constant number of electron vacancies per atom. The electron vacancy numbers N,. used were originally the same as those in the Pauling theory, but were later modified empirically vn order to bring about better agreement with data for the p phase in certain ternary systems. For alloys, N,, was calculated on the assumption of simple additivity from the electron vacancy numbers of the components, as follows: N,. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2 (Fe) + 1.71 (Co) + 1.6 (Ni). On this basis a reasonably constant value of N, = 3.4 was obtained for all of the binary u phases and a fairly constant value of N,, = 3.1 for the various p phases. More recently, Bloom and Granta pointed out that a similar correlation with the total number of 3d and 4s electrons per atom is also fairly well fulfilled and concluded that no reference need be made to the Pauling theory. This proposal does not lead to the same binary a compositions as the one described above, so that the relative merits of the two proposals may be determined on the basis of direct comparison with experimental composition data. The purpose of the present paper is to provide such a comparison. Since the experimental data for the composition ranges of several of the known u phases were rather incomplete, it was decided to carry out new experimental determinations for many of the binary systems. Experimental Procedure The alloys were prepared by induction melting in recrystallized alumina crucibles, either in vacuum or in helium atmospheres. Some aluminum was picked up from the crucibles in the alloys of high vanadium content, but this was minimized by keeping the alloys in the molten state for as short a time as possible. The maximum aluminum impurity was 0.13 wt pct by chemical analysis, in an alloy containing over 50 wt pct V. In general, the as-melted compositions agreed accurately with those obtained by chemical analysis. In the case of manganese, however, losses inevitably occurred; consequently all manganese alloys were analyzed. Specimens of all alloys were annealed at temperatures ranging from 1000" to 1300°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. All manganese alloys were sealed in quartz tubes under vacuum before annealing. The specimens were held at temperature for between four and eight days before being quenched into cold water. Alloys were prepared for microscopic examination by mechanical polishing, usually followed by electrolytic etching. X-ray diffraction specimens were prepared by crushing the homogenized alloys, and by reanneal-ing the obtained powders in evacuated quartz tubes for a few hours at the temperature of the lump anneal. X-ray diffraction patterns were made with unfiltered chromium radiation, using an asymmetrical focusing camera of high dispersion. Using microscopic and X-ray techniques jointly, the accuracy

Jan 1, 1955

By Eugene A. Mizikar

A mathetnatical model of heal transfer in continuously cast steel slabs is described. The model, consisting of a unidimensional transient conduction equation and boundary condition equations, has been pvogrammed for computer solution. Temperatuve and solidification profiles calculated for a 6-in. slab, being cast under several conditions of secondary cooling, are presented and compared. Calculated solidification profiles are in agreement with reported expevinle~ztal values. For the mold zone, the predicted slab shell thickness can be described by: Resuilts of the study indicate that multibank spray cooling followed by radiant cooling should be employed when solidifying thick slabs with minimum surface temperature of 1600°F. Under these conditions, a 6-in. slab can be expected to solidify in about 8.3 min. Computer results also indicate that radiant cooling can replace spray cooling during solidification of the final 30 pct of slab with little increase in overall solidification time. CONTINUOUS casting has come to the forefront of the steel industry in recent years because of economic advantages resulting from increased yields and elimination of several processing steps. Considerable work, however, remains to be done regarding modifications to the process and operating procedures. Both a lack of operating plants in this country and the experimental difficulties associated with direct measurements on moving castings have made determination of solidification rates and temperature distributions difficult. An alternate approach is to mathematically simulate heat transfer in a continuously cast section, and then calculate the temperature distributions as a function of the controllable variables of the process. Simulation of heat transfer during solidification requires that a nonlinear mathematical problem be solved. As pointed out by Ruddle,' there are two mathematical approaches to the problem- the analytical approach and the numerical approach. While the analytical approach is certainly the more elegant of the two, it does require a number of inexact assumptions because of the complexity of the problem. For example, noteworthy analytical treatments of heat transfer in continuous casting have been developed by Savage Hills,3 and pehlke4 only by making one or more simplifying assumptions such as invariant thermophysical properties, constant heat-transfer coefficients in the mold, and linear temperature profiles in the shell. Simplifying assumptions such as these can introduce considerable uncertainty in the validity of results calculated with analytical solutions. Numerical solutions, which are considerably more versatile, appear to be better suited for solving solidification problems. Complex variations in the boundary conditions and variable thermophysical properties can be handled readily with this technique. Whereas numerical computations can be long and tedious when done by hand, results can now be obtained quite rapidly with the use of either the digital or analog computer. Several numerical models of heat transfer in continuous casting have been published. In 1963, Adenis, Coats, and Ragones published a numerical model used to calculate temperature distributions in direct-chill-cast magnesium billets. More recently, Donaldson and Hess 6 presented results obtained with a numerical computer model of heat transfer in continuously cast steel billets. In the present study, a model of unidimensional heat transfer in continuously cast slabs is presented. The method of solution on a digital computer is also included. Calculated temperature distributions and solidification profiles for various schemes of secondary cooling along with attempts to verify the model are also discussed. MATHEMATICAL MODEL The schematic representation of the slab continuous casting process in Fig. 1 illustrates that the slab passes through three distinct zones of cooling. Accordingly, the mathematical model consists of three parts: 1) solidification in the mold; 2) solidification in the spray cooling zone ; 3) solidification in the radiant cooling zone. Heat-Transfer Equations. The model was developed bymaking a heat balance on a horizontal slice of slab over the time period required for the slice to proceed from the liquid metal meniscus in the mold to the cutoff station. As shown in Fig. 2, the imaginary slice extends from the center line to the surface of the slab. As the slice moves downward, heat is conducted from the center line to the surface of the slab at a rate governed by the surface boundary condition and thermophysical properties of the metal in the slice. The following partial differential equation describes the conduction of heat in a medium moving at velocity U in direction Z:

Jan 1, 1968

By J. D. Defilippi, E. M. Gilbert, K. G. Brickner

FCC chromium-manganese-nitrogen (Cr-Mn-N) steels differ from most other fcc materials in that these steels undergo a ductile-to-brittle transition. Transformation to martensite is considered to be responsible for this behavior in some metastable Cr-Mn-N steels. However, very stable Cr-Mn-N steels also exhibit a ductile-to-brittle transition. The results of this study indicate that deformation faulting is the probable cause of the brittle behavior of stable Cr-Mn-N steels. Deformation faulting accounts for the ductile behavior of these steels in a tension test at -320°F and brittle behavior in an impact test at -320°F. Deformation faulting also accounts for the toPological features observed on the fracture surfaces of impact specimens of these steels. FACE- centered- cubic chromium-manganese-nitrogen (Cr-Mn-N) steels differ from most other fcc materials in that these steels undergo a ductile-to-brittle transition. Many Cr-Mn-N steels transform to martensite during deformation,l-5 and several investigatorsl-3 have suggested that the brittle behavior of these steels is caused by martensite formation. However, very stable Cr-Mn-N steels also exhibit brittle behavior. Schaller and Zackeyl reported that a very stable Cr-Mn-N steel (less than 3 pct martensite formed at -320°F) exhibited a transition temperature higher than that for steels in which large volume fractions of martensite formed during testing. The explanation given by Schaller and Zackey for this observation was that in the very stable steel the martensite, because of its higher interstitial content, was more brittle than that formed in their other steels. This explanation was questioned by Tisinai and samans4 and Baldwin.6 Moreover, because the toughness of stainless martensite at cryogenic temperatures is generally very low, this explanation does not account for Thompson's7 observation that small additions of nickel (1 to 3 pct) greatly improve the toughness of high nitrogen (0.35 pct) Cr-Mn-N steels. The present paper summarizes the results of an investigation of the low-temperature brittleness in very stable Cr-Mn-N steels. The importance of the mode of deformation on the toughness of these steels is discussed. Table I. Compositions of the Steels Invertigated, Pet Steel C Mn P S Si Ni Cr N - A 0.09 14.70 0.018 0.011 0.47 0.22 18.40 0.54 B 0.12 14.90 0.001 0.008 0.48 0.14 17.80 0.38 C 0.12 14.95 0.004 0.005 0.62 3.95 18.43 0.38 MATERIALS AND EXPERIMENTAL WORK The compositions of the steels investigated are shown in Table I. Steels A and B had compositions within the limits of a proprietary Cr-Mn-N stainless steel,* whereas Steel C was similar in composition to the proprietary steel except for its 3.95 pct Ni content. All steels were hot-rolled to 1/2-in. thick plate. The plates were subsequently annealed for 1 hr at 2000°F and water-quenched. Standard longitudinal and transverse Charpy V-notch impact specimens were machined from the annealed plates. Duplicate longitudinal and transverse impact specimens were tested at 212", 80°, 32", 0°, -100°,-160°,-200°,-256", and -320°F. Longitudinal tension-test specimens were also machined from the plates and tested at a crosshead speed of 0.05 in. per min at the aforementioned temperatures. The fractured impact and tension-test specimens of all three steels were examined to determine whether martensite had formed during testing. Magnetic, X-ray, electron-diffraction, and electron-microscopy techniques were used to detect the presence of martensite in the highly deformed areas of these specimens. Metallographic examination of highly deformed areas of impact and tension-test specimens revealed the presence of dark-etching bands, such as those shown in Fig. 1. These bands were observed only in deformed samples and were thought to be associated with the low-temperature brittleness of the Cr-Mn-N steels. Accordingly, a sample 1 in. wide by 3 in. long was cut from the 1/2-in.-thick plate of Steel C. This sample was surface-ground to a in. and then cold-rolled 60 pct at -320°F. Thin foils were prepared from the cold-rolled sample and examined in a JEM electron microscope. Brightfield, dark-field, and selected-area diffraction techniques were used to determine the cause of the dark-etching bands. Fractographic experiments were also performed. Impact specimens Of Steels A, B, and C were broken at -320oF, and the fracture surfaces of these specimens were immediately shadowed with carbon. The carbon replicas were examined in a Siemens electron microscope, and attempts were made to correlate the topological features of the fracture surfaces with the deformation mechanisms that could be occurring during an impact test of these steels.

Jan 1, 1970

By C. S. Samis, J. C. Mitchell

Sodion activity data have been obtained for the Na-A1 system for sodium concentrations in aluminum between NN, = 25 . 10-and 300 x 10'. This concentration intert-a2 encompasses those sodium concentrations nor1)zally encountered in aluminum reduction cell operation. The sodium activity data were measured by a two-phase equilibration of sodium between a lead and an aluminam rich phase. The Na-Pb system was emplojed as a reference for the determination of the actiz7itj 0.f sodium. The activity of sodiin in aluminuwz exhibits large positi2.e deviations frorn ideality and a strong dependence, on concentration below NN, = 100 x 1K6. The inteated data indicate that the activity of aluminium is equal to its mole fraction over the range of miscibility of the Na-A1 sgstem. The data on the Na-A1 binary have been combined with experimental data on the cryolite-A1 system at 1025°C to obtain the activities of Na F and AlF, in liquid cryolite oz2er the cornposition 1-ange encountered in aluminum cell operation. The results are in agreement with activities calculated from the NaF-AlF, phase diagram. ALUMINUM is produced commercially by the electrolytic reduction of aluminum oxide dissolved in molten cryolite. There is considerable controversy over the actual mechanism of the discharge processes, but sodium potentials in the systems appear to play an important role in the reduction mechanism. The metal-salt reaction involving NaF and aluminum to produce A1F3 and sodium is responsible for the presence of sodium in the aluminum metal phase. Additional sodium may be produced from the simultaneous deposition of sodium and aluminum at the cathode as a result of a cathodic overvoltage. runert' has suggested that sodium gas at atmospheric pressure would be the result of reaction between cryolite and aluminum at 1000°C. Subsequent investigations have shown that production of sodium at atmospheric pressure does not occur. These later investigations can be conveniently separated into two categories. The first involves sodium, aluminum, and cryolite, in which the sodium activity was measured. The second includes a lead phase for sodium activity measurement. Jander and errmann,' studied the reaction: at 1090°C in alumina crucibles under an atmosphere of dry, oxygen-free nitrogen. The equilibrium constant for the reaction was expressed in terms of concentration. Their results in Fig. 1 show an increase in sodium content of the aluminum with increasing NaF/A1F3 weight ratio. Pearson and waddington3 performed similar experiments at 1000°C. Their results are included in Fig. 1. Dewing and ollinshead have measured the sodium content of aluminum as a function of the NF/AF, ratio at 1025"C, Fig. 1, and ewin' measured the sodium content of the aluminum in a system involving the solid reactants NaF, cryolite, and liquid aluminum. This reaction is different from those discussed above. Two solid phases, NaF and Na3A1F6, and a liquid aluminum phase were present. The sodium concentration in the aluminum was determined by the temperature. Dewing's measurements covered the temperature range 679" to 896°C. Omo, Matsushima, and 1t02" investigated the equilibrium 6NaF ential thermal analysis. Stokes and Frank6 determined sodium activities by

Jan 1, 1970

By C. H. Lee, R. Maddin

The diffusion rates of Ag110 in cylindrical single crystals of 99.99 pct pure silver, which were twisted to a total surface strain of 0.91 during the diffusion anneal at temperatures of 700°, 750°, and 800°C, were measured by sectioning and counting as a function of the strain rates. The ratio of the diffusivities while strain ing occurred (Ds) to those of the unstrained specimens varies linearly with the rate of twisting and attains values of near 100 for some of the rates used. The enhancement of diffusion by straining is inversely proportional to the temperature at which diffusion occurs. The activation energy for diffusion determined from the data plotted as a function of the rate of twisting decreases from 44,090 cal per mole for zero strain, to an asymptotic value of 21,000 cal per mole for the strain rates of 22 x it)"5 see-l. Qualitative explanation for the observations based on the generation of nonequilibrium number of defects by plastic deformation will be discussed. The initial research of Buffington and cohen1 on self-diffusion in a iron under compressive stresses contributed the first quantitative information concerning the effect of applied stresses on diffusion. These results were obtained from radioactive Fe55 plated on one of the horizontal surfaces and compressing the large-grained specimens while the diffusion-anneal was occurring. Enhancement of diffusion of a maximum of seventeen times was observed provided the strain was in the tertiary stage of creep and the rates of straining were at least as fast as rates used in the normal creep test. On the other hand, Darby, Tomizuka, and Balluffi,2 extending silver single crystals up to 30 pct elongation at rates of straining about equal to those used by Buffington and Cohen observed no effect. For the past two and a half years at the University of Pennsylvania, we have been investigating the effect or torsional strains on self-diffusion in silver single crystals. If enhancement is observed as has been reported1 a possible explanation may be based upon the generation of fairly large numbers of point defects and their role in the diffusion process. Hence, since torsion should produce an abundance3 of point defects, an increase in the diffusivity while the crystal is being twisted should easily be measured. EXPERIMENTAL PROCEDURE Our research uses single crystals of silver prepared from 99.99 Ag by the Bridgman method in a dynamic vacuum of less than 25 µ. As grown, they are about 25 cm long by 1.3 cm in diam. The crystals are cut into 7.5 cm lengths with a jeweler's saw and machined to the shape shown in Fig. 1. The test length of the crystal is machined to a 0.6 cm diam after which the ends are masked and the test section etched heavily in HNO3, and KCN:(NH4),S2Os , solution to remove the effects of machining. The specimen is then annealed in vacuum for 8 to 12 hr at 800°C to remove any residual stresses and also to recrystallize the end sections. The recrystallized ends are necessary since experiments showed that single-crystalline end sections are too soft to transmit the desired torque. Occasionally, recrystalliza-

Jan 1, 1960

By R. G. Robins, O. J. Kwok

The application of chemical thermodynamic theory to high temperature aqueous systems is discussed as a basis for the explanation of thermal precipitation. The derivation of high temperature potential/ pH diagrams is briefly outlined in order to show a temperature/pH relationship for hydrolytic precipitation, which is an effect that is caused simply by heating an aqueous solution. Various examples of thermal precipitation are given, with particular reference to separation of metal values from leach solutions. Metal sulphate solutions are shown to precipitate basic sulphates, hydrated sulphates , oxides, hydroxides, and oxydroxides of the metal depending largely on the pH, the concentration of metal ion, and the concentration of sulphate or bisulphate. The CuS04-H2S04-H20 system is treated in some detail, and the separation of copper from other metal ions is investigated. Other separations involving Fe, Ni, Zn, Cd, and Cr are considered. Other advantages of thermal precipitation, such as the formation of high purity, large particle size and easily filterable materials, are presented. The kinetics of thermal precipitation are also briefly examined.

Jan 1, 1973

By Frank F. Poland

TEE purpose of this paper-is to describe a new process for the refining of secondary copper-base metals and a specially designed high-temperature electric-resistor furnace used in the process for the distillation of zinc from these metals. The process was used for the conversion of nickel silver to cupronickel and to recover the zinc content in metallic form. It also proved applicable and economical for the treatment of scrap brass for separating and reclaiming the copper and zinc. The relatively large furnace developed for the distillation of zinc is described in detail, for it made economically possible the direct recovery of metallic zinc from scrap brass, which is a new step in the processing of such material. Considerable interest has been shown in the utilization of the distillation furnace for other metallurgical processes, where it is of advantage to operate in a controlled neutral or reducing atmosphere, or to avoid having the processed metal in contact with refractories other than carbon, or to operate at temperatures between 3000 and 4000°F. PURPOSE OF DEVELOPMENT It was recognized early in the war effort that nickel would become a critical metal, therefore all nickel stock and alloys containing relatively high percentages of nickel were frozen immediately. Among these alloys were considerable quantities of various grades of nickel silver, an alloy containing copper, nickel, zinc, and in some grades lead, also minor amounts of iron, manganese and other constituents. At the time there was no existing plant or process to eliminate the zinc, lead, and minor constituents so as to convert this metal to cupronickel, one of the important alloys needed by the U. S. Navy for condenser parts. Therefore the Bureau of Industrial Conservation of the War Production Board requested the executives of the leading nonferrous metal companies to have their metallurgical staffs study the problem of converting this metal to cupronickel conforming to U. S. Navy Specification 44T40. The composition specified therein is as follows: nickel, 29 to 32 per cent; zinc, 1.00; iron, 0.00 to 0.60; lead, 0.05; tin, 1.20; manganese, 0.00 to 1.00; total of other elements (maximum), 0.50; copper, remainder. The problem in converting these alloys to cupronickel was the elimination of zinc, lead, iron, manganese, and other elements without appreciable loss of nickel to slags or other by-products. Revere Copper and Brass Incorporated, through its Research and Development Department, undertook to solve this problem. A Government-owned plant was built at Rome, N. Y., and there the con- version was successfully made.

Jan 1, 1946

By D. M. Warner, Samuel Daniels

In this paper are given the mechanical properties, determined by the Engineering Division, Air Service, U. S. A., of the 94 per cent. aluminum, 5 per cent. copper, 1 per cent. silicon alloy as 8and-cast and as heal-treated commercially to Air Service Specification No. 11,300. This particular alloy was tested both in the cast and in the heat-treated condition. Tension and tension modulus values were obtained from machined and from un-machined test specimens; while data for shear, compression, impact, torsion, and for Brine11 and Rockwell hardness were found from machined bars. Specific-gravity tests were made on sanded, un-machined specimens. The metallography of the alloy is useful as a control to heat treatment and presents some interesting peculiarities in regard to the two iron-bearing compounds. The demand for an aluminum alloy, suitable for sand castings, that may be heat treated to meet requirements of high strength, ductility, shock and corrosion resistance, and ready machineability has led to the commercial development of a proprietary material that contains from about 4 to 5 per cent. of copper, 1 per cent. of silicon, and such impurities as iron, up to a maximum of 0.75 per cent., and manganese, in quantity usually less than 0.1 per cent.' Magnesium is not generally present, for it tends to nullify the beneficial influence of the added silicon by forming magnesium silicide. The function of the silicon is to minimize casting difficulties and, structurally, to favor the precipitation of (insoluble) iron-bearing skeletons rather than the needles, which prevent full realization of tensile properties from heat treatment by stimulating intergran-ular fracture. The amount of silicon necessary to counteract the ill effect of iron is equal to or slightly more than the content of iron; the excess of silicon over this ratio, under certain conditions of heat treatment, enters with CuAl2, the principal hardening constituent, into solid solution and contributes somewhat to the strength of the alloy without appreciably impairing its ductility. The schedule of heat treatment of this alloy depends on the design (cross-sections) of the castings and on the nature of the tensile properties desired. Essentially, the process consists in heating the material at about 950" F., quenching in oil or in cold or boiling water, and artificially aging

Jan 1, 1926

The American Society of Mechanical Engineers extends an invitation to members of the Institute to participate in an exceedingly interesting excursion on Saturday, November 11. Permission has been secured for a visit to the plant of the Electric Boat Co. at New London, Conn. There will be run a special-test on a high-power 8-cylinder, 4-cycle Diesel engine. A large number of submarine and other engines in various stages of construction will be seen, also the boring of torpedo tubes, cylinders and other equipment for submarines. The drafting rooms and foundry mill also be open for inspection. The party will have an opportunity to see at close range the submerging of several submarines, and an attack on a vessel on the surface, an exhibit which is being arranged by courtesy of Rear Admiral A. W. Grant, who is in command of the submarine forces of the United States. The Boston members will leave South Station on train No. 7 at 8.30 A. M. Those from Providence will board this train at 9.36 A. M. The Worcester members will leave on train No. 745 at 8.36 A. M. The New York contingent will leave the Grand Central Terminal at 8.31 A. M. on train No. 8. This train will leave New Haven at 10.30 A. M. Upon arrival at New London, each group will go directly to the Mohican Hotel, where a "get-acquainted" luncheon will be served

Jan 10, 1916

By W. H. Bassett

A 10-year, sea-water, corrosion test of tubes of several copper alloys has shown that many alloys withstood attack by solution, pitting, and dezinkification; a 1-year, salt-spray test of sheet-metal specimens of the same composition showed the same results. THE late J. P. Sparrow, chief operating engineer of the New York Edison Co., carried out a series of practical tests on condenser tubes of several copper alloys and reported on the results to the Association of Edison Illuminating Companies at its meeting in' September, 1913. In the preparation of these tubes the senior author had the pleasure of cooperating. Copper-zinc alloys in the proportions of 60-40, 70-30, 80-20, 90-10, and Admiralty metal, which is in effect 70-30 with 1 per cent. of tin, were tried. Monel metal and several copper-nickel alloys, and 8, 5, and 3 per cent. aluminum bronze were also tried. At the time of this report, the aluminum bronze had been in service for 4 1/2 years and seemed to be giving especially good results but later it began to fail and showed no substantial improvement over Admiralty metal. Monel metal was unsatisfactory and the nickel alloys apparently did not give better service than the Admiralty alloy. Previous to the publication of the report, and after considerable discussion, it was agreed that a test where tubes of different kinds could be under laboratory observation would be advisable, so the apparatus described here was set up in The American Brass Co.'s Waterbury Laboratory. This was fitted with tubes of copper, brass, bronze, nickel silver, cupro-nickel and other alloys, and the test started Oct. 11, 1912. Salt water from East River, New York harbor, was barrelled and transported to the laboratory for the test. A fresh supply, completely replacing the water in service, was obtained at the end of each six months period.

Jan 1, 1925

By C. W. Gibbs, E. K. Parks

In 1929 the Standard Oil Company of California commenced the development of a device for obtaining temperatures and pressures in flowing and shut-in wells and of suitable running equipment for such a recorder. Although simple in principle, the recorder has required much experimental work in its development. The various problems have now been solved to such an extent that it is believed that the apparatus affords a sturdy and reliable means for obtaining information regarding depth pressures,—apparatus that may be turned over to a well gang for routine operation. As an example of the rough usage the device will withstand a recent incident may be cited. Owing to failure of the lowering line at the conclusion of a run a recorder was dropped some 6300 ft. through 2 1/2-in. tubing filled with gassy oil. The device was fished out undamaged and with the pressure record intact, although the instrument had been subjected to a pressure greater than 2300 lb. per sq. in. for some 24 hr. after impact at bottom. Description of Recorder The instrument is of the continuous recording loaded spring type (Fig. I). Temperature is not recorded continuously but is obtained by maximum recording thermometers in an auxiliary thermometer well. The entire instrument assembly, from bottom of the recorder to top of the socket, is 6 1/2 ft. long and weighs less than 25 lb. The maximum outside diameter of the recorder shell is 1 1/4in., and all attachments need be no larger. This permits lowering the device inside 2-in. tubing. The operating principle is simple. The well pressure acts upon a piston A resisted by the extension of spring B. The spring deflection is recorded by a stylus C upon paper within the recording drum D. Springs.—To improve accuracy at lower maximum well pressures five interchangeable spring assemblies are used. These have maximum pressure ranges of from 250 to 5000 lb. per sq. in. Piston diameter is the same in all cases, and each spring is designed for a deflection of about 5 in. for maximum pressure loading. A complete spring assembly there-

Jan 1, 1934