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By Luiz C. Correa da Silva, Robert F. Mehl

An experimental study of the movement of markers in the systems Cu/a-brass, Cu/Sna-solid solution, Cu/Ala-solid solution, Cu/Ni, Cu/Au, Ag/Au, employing many types of markers and a variety of temperatures. Marker movement is confirmed and undoubtedly associated with the manner in which atoms move during diffusion. EVERAL years ago Smigelskas and Kirkendall' •S reported measurements on the interdiffusion of copper and a-brass and on the movement of inert markers placed at the original join. These markers were observed to move toward the a-brass side of the join, and from this it was inferred that zinc diffuses in a-brass more rapidly than copper. Similar results were reported a little earlier for the diffusion of solvents into high polymer solids.' This has attracted much attention, particularly from those interested in the mechanism and the theory of diffusion: Seitz3 has employed it in supporting the vacancy theory of diffusion; from the data Darken4 has calculated separate diffusion coefficients for copper and zinc, developing a "phenomenological" theory of diffusion; and Bardeen5 has employed it in constructing a general theory, including therein the work of Seitz and Darken, as has Le Claire. These matters have recently been reconsidered in a sympo~ium.7 Some reason has existed for questioning the work of Smigelskas and Kirkendall.' Their technique consisted in electroplating copper on a-brass, upon the surface of which Mo-wires had been secured, and then diffusing, measuring the extent of diffusion along the normal to the join, and measuring the marker displacement in the same direction by a comparator determination of the distance between Mo-wires on opposite sides of the electroplated brass sample. It has been suspected that the copper plate might have been porous, and that the original interface might have been an imperfect join, both contributing to the transfer of the volatile zinc by vapor transfer;' it has also been questioned whether the marker movement might not in a measure be a property of the marker itself; etc. These legitimate questions require experimental answers; the present paper offers such answers. Moreover, Smigelskas and Kirkendall studied the effect only in the Cu-Zn system and at one temperature; the attention which the work of Smigelskas and Kirkendall has commanded recommends similar

Jan 1, 1952

By H. H. Stout

IN the early fall of 1025, the writer was conducting, in the Ledoux and Co. labora-tory, New York, experiments directed to-ward ascertaining the effect on its impurity content when cathode copper was subjected to a current of various gases at an elevated temperature below the melting point. The apparatus consisted of a vertical I-in. dia. silica tube about 12 in. long, heated on the outside. The cathodes were broken to pass 3/8-in. mesh, and a current of various differ-ent gases was passed up through a 4-in. long column of these loose cathode particles in the vertical tube furnace. Temperature was maintained to 1500° to 1600°F. and the gas treatments lasted from 3 to 6 hr. The writer observed that whenever reducing gas (H2 or CO) was used, these cathode par-ticles stuck together at points of contact with each other. The cohesion was so marked and tenacious that an examination was made of the fractured surfaces, when cathode particles were broken from the cluster. Crystal growth was always found to have taken place across the surfaces where separate particles were in contact, but only after all oxides, sulphates, etc., had been completely removed. The idea of a possible new process was then conceived and was disclosed to A. M. Smoot (V. P. Ledoux and Co.) with intent to obtain his views. The first conception as given Smoot was "to gas-clean broken cathodes, put them in an extrusion press, solidify and extrude them at around 1500°F." Smoot's reaction, after a few moments considera-tion, was, "It looks perfectly all right to me." The writer and his assistants, W. H. Osborn and H. H. Stout, Jr., after confer-ring as to ways and means, decided to go ahead with preliminary laboratory experi-ments, which, it was thought, would move the new process from the possible to the probable. This program followed a course indicated by three basic considerations: I. Since brittle cathodes were often unin-tentionally produced, it seemed probable that the laws controlling this type of deposi-tion could be ascertained. 2. We had already proved the gas-clean-ing feature. 3. There remained to prove: whether a sound, homogeneous metal billet could be produced with crystal growth established over the entire surface of each individual particle in the billet; and, if so, what would be the physical properties? Osborn arranged with Columbia Uni-versity for conducting experiments in its research laboratory to prove or disprove the third item; Columbia assigned C. A. Phillipi, Jr. to assist in the project. A press with a cylinder 2 in. high and of I-in. dia. was used. It was surrounded and heated by a resistance coil of Nichrome wire. Broken tough cathodes were used.

Jan 1, 1940

By R. F. Mehl, M. Gensamer

Although a large number of X-ray photograms of cold-rolled steel have been published, two circumstances have led to the experimental work reported in this paper. The first is that no complete study, making use of the pole-figure method of Weverl, has been made of cold-rolled low-carbon steel. Wever has published pole figures of mild steel subjected to plane parallel deformation1, 2 and undoubtedly he has applied the method to cold-rolled mild steel, but the authors have not found these data published. Kurdjumow and Sachs3 have applied the method to the study of rolling and recrystallization textures in electrolytic iron; their results will be referred to later. The reason for this dearth of papers using the pole-figure method is obvious; a greater number of photograms and more analytical work (although this work is quite simple and straightforward) are required to construct a pole figure than most investigators have felt worth while, despite the fact that no other method of which the authors are aware will satisfactorily depict the orientations of the crystallites in a polycrystalline aggregate. The second circumstance that led to the work reported in this paper was the appearance of a paper by Wayne A. Sisson4 on the same subject. In his valuable study of the factors influencing the development of preferred orientations in cold-rolled mild steel, Sisson made one observation that required confirmation; that is, that at some stage of the rolling process the type of preferred orientation changed from the type that gives a photogram characterized as a "six-point" X-ray pattern to that known as a "four-point" pattern. A similar observation had been made by Tam-mann and Heinzel5, who studied the orientations developed in the rolling of steel by the specular reflection of light from the etched surface of rolled samples. These workers also found that the type of preferred orientation changed during the rolling process. The authors had some difficulty in seeing how this behavior could be consistent with modern views on the genesis of preferred orientations, particularly with those of Wever2

Jan 1, 1936

By Walter Kauzmann

All viscous or plastic flow of incompressible matter is the result of shear strain; the changing shape of any body that is being plastically deformed can be completely described in terms of the shear strain occurring at each point in the body.† Furthermore, the relative amounts of shear strain occurring in different parts of a body under stress depend upon the relative rates of shear strain at those different points, so that if the dependence of the shear rate of any material on the temperature, shear stress, previous history, etc., were understood, the principles of plastic deformation would be known, and we could calculate how a body made of a given material, having a given shape, and subject to a specified system of forces, would change its shape with time. It may be said, then, that the problem of plasticity resolves itself into, first, the problem of the rates of pure shear processes, and second, the application of what is known about pure shear to actual cases. It is the purpose of this work to investigate the former problem —i.e., the dependence of shear rates on temperature, stress, etc.—from the standpoint of .recent developments in the field of chemical-rate theory and with particular reference to the phenomena occurring in the creep of metals and in the plastic flow of crystalline solids in general. It is left for the mechanical engineer, and perhaps the expert in hydrodynamics, to deal with the problem of app1ications.l Resolution of Macroscopic Shear into Microscopic Movements; Resemblance to Chemical Reactions Just as any large body is made up of many small units, or atoms, so macro-scopically observable shear is the result of many microscopic unit shear processes; just as the understanding of the behavior of large bodies demands the understanding of the atoms of which it is made, so the understanding of macroscopic shear demands the understanding of these fundamental unit processes. The study of shear from this "atomistic" point of view has made considerable progress. There has been fairly complete understanding of shear processes in gases for a long time, at least for non-turbulent flow, as a chapter on gaseous viscosity in any text on the kinetic theory of gases will prove' In recent years Andrade2 and Eyring3 have presented important theories for the flow of liquids and amorphous solids. Becker14 Orowan,5 Taylor,6 Burgers,7 and Kanter8 have considered the plastic flow of crystalline solids from this

Jan 1, 1941

By Charles Miller

Natural carbon dioxide has recently been exploited in the United States in consequence of oil and gas developments in the Western States and the growing demand by transcontinental and transoceanic shippers for solid carbon dioxide. The discovery by drilling of commercial deposits resulted in consideration of its geographic and geologic distribution and occurrence. Its wide distribution in nature is evidenced by its occurrence in the atmosphere, hydrosphere and lithosphere. The question of origin of carbon dioxide involves consideration of theories similar to those concerning natural hydrocarbons, although available evidence favors an inorganic rather than an organic source. Areas favorable to development of commercial production appear to be those in proximity to igneous rocks or in the vicinity of decadent volcanic activity, where, it has long been known, the gas is evolved either free or dissolved in the waters of fumaroles, geysers or mud pots. Structure contour maps are presented showing the Wagon Mound anticline in New Mcxico and the Farnham anticline, Utah. A well drilled on the latter supplies gas to a 20-ton plant manufacturing solid curbon dioxide at Wellington, Utah, on the Denver and Rio Grande R.R., whence it is shipped to surrounding territory and to the West Coast. Before funds are invested in a plant for the manufacture of liquid or solid carbon dioxide, whether supplied by wells or springs, an effort to ascertain the volume of gas available is advisable. The use of present methods of estimation of gas reserves with modifications to account for the quantity absorbed by any water present in the producing formation is recommended. The Farnham anticline is used as an example and computations are made of the probable volume of gas originally present in the structure. No attempt was made to compute reserves in the Niland area, California, for the reason that in such areas it is believed the volume is indeterminate. Introduction Carbon dioxide, in liquid and solid form, has found a wide variety of uses other than its primary application in carbonating beverages. It is now used in more than 40 different ways, ranging from cooling or freezing to use in gas or liquid form for mechanical purposes, chemical industry, explosive, fire extinction, and tire manufacturing. Undoubtedly the chief supply of carbon dioxide is obtained from industrial plants or artificial sources and until recently natural deposits of the gas have received little consideration. Few will question the utility and perhaps dependability of artificial sources, which possess the advantage over

Jan 1, 1938

By Herbert H. Uhlig

Although the mechanical properties of high-carbon manganese-iron alloys, particularly the Hadfield manganese steels, have been established, the literature discloses discrepancies in the reported properties for the low-carbon alloys. Hadfieldla summarized the existing data up to 1927, including the investigations of Guillet, Arnold, Strauss, Burgess and Aston, and reported his own values for alloys containing for the most part from 0.06 to 0.I5 per cent carbon. He noted: From these comparisons it wil! be seen that while there is a broad and general agreement as to the character of the alloys at the different manganese percentages, there are disparities in individual cases, especially as regards the degree of toughness or brittleness displayed by an alloy with certain percentages and with particular types of treatment. These differences are not always readily explainable.lb His data showed that alloys containing 4 to 10 per cent manganese water-quenched from Iooo°C. were brittle and hard with maximum brittleness at about 7 per cent. Slight improvement in ductility was obtained with compositions from 10 to 17 per cent manganese. Alloys containing up to 17 per cent manganese slowly cooled rather than quenched from 87o°C., he found, were slightly improved in ductility with significant improvement in alloys analyzing 4.1 and 4.8 per cent manganese. Recently Walters, Kramer and Loring2 reported mechanical properties for alloys made up from electrolytic manganese and ingot iron and containing from 0.02 to 0.04 per cent carbon. They showed that a tempering treatment at 54o°C. (Iooo°F.) for one hour significantly improved the ductility of compositions ranging from 6.7 to &apos; 20.7 per cent manganese. The differences of these compared with Hadfield&apos;s results they considered to originate in this tempering treatment plus the fact that Hadfield&apos;s alloys contained higher carbon and phosphorus (0.06 to 0.I5 per cent C; 0.06 to 0.07 per cent P compared with 0.02 to 0.04 per cent C, <o.ooI per cent P). In this paper it is shown that of the low-carbon alloys (0.02 to 0.03 per cent) containing from 3.3 to 21.5 per cent manganese moderately or rapidly quenched from IOOO°C. some are brittle or ductile, depending on presence or absence of hydrogen. Hydrogen is readily absorbed at high temperatures, and much of it is retained when the alloys are cooled to room temperature. The presence of hydrogen in the range of composition from 10 to 18 per cent manganese is a major factor in determining relative ductility. At 22 per cent manganese, and also at compositions below 10 per cent manganese, factors other than or in addition to hydrogen play a role. These are discussed. Also data are presented to show that hydrogen absorbed by the high-carbon alloys of Hadfield composition is without effect on their mechanical properties.

Jan 1, 1944

By A. C. Fieldner, Lester L. Hirst, Henry H. Storch

Experimental work on liquefaction of coal was taken up by the Bureau of Mines in 1936 when it became evident that a prudent policy from the national point of view should include preparation for the time when gradual exhaustion of petroleum resources would require supplementing the growing demand for motor fuel with gasoline and diesel oil from coal. At that time (1936) certain foreign nations that had no home sources of petroleum, especially Germany, England, and Japan, were conducting active research and at least two of them were producing liquid fuel from coal on a commercial scale. Germany was reported to have an annual producing capacity of 800,000 metric tons of gasoline per year, and England had just put into operation the Billingham plant of Imperial Chemical Industries for the hydrogehation of bituminous coal and tar by the Bergius-I.G. process. The annual capacity of this plant was about 150,000 long tons of gasoline per annum (3500 bbl. per day). With these developments taking place in foreign countries, it seemed important to undertake a long-range program of fundamental research in this country to establish a sound groundwork for the evaluation of foreign work on synthetic liquid fuels and at the same time to obtain data on the oil yields and operating difficulties using various kinds of American coals and lignite to the hydrogenation process. The results of such research would be useful in determining the yields and quality of liquid products obtainable from various coals so that American industry would be in position to select the most suitable coals and make rapid progress in establishing this new industry when the commercial need should arise. It was hoped, also, that progress in a better understanding of the chemistry of coal hydrogenation would reduce the cost of the process materially. To carry out this program, a small continuous unit capable of hydrogenating 100 Ib. of coal in 24 hr. was installed at the Central Experiment Station of the Bureau of Mines at Pittsburgh, Pa. Small steel autoclaves or bombs of 0.3 gal. (1.2 liters) capacity also were used for batch-hydro-genation experiments in the study of the chemical fundamentals of the process. Much valuable assistance was obtained in planning the experimental program and designing the equipment from the Fuel Research Station of Great Britain and the Fuel Laboratories of the Mines Department of Canada, where such investigations had been in progress for several years. Equipment and General Procedure of Research The industrial liquefaction of coal by the Bergius-I.G. hydrogenation process as practiced at Billingham, England, from

Jan 1, 1944

By A. R. Gregory

A shear wave velocity laboratory apparatus and techniques for testing rock samples under simulated subsurface conditions have been developed. In the apparatus, two electromechanical transducers operating in the frequency range 0.5 to 5.0 megahertz (MHz: megacycles per second) are mounted in contact with each end of the sample. Liquid-solid interfaces of Drakeol-aluminum are used as mode converters. In the generator transducer, there is total mode conversion from P-wave energy to plain S-wave energy. S-wave energy is converted back to P-wave energy in the motor transducer. Similar transducers without mode converters are used to measure P-wave velocities. The apparatus is designed for testing rock samples under axial or uniform loading in the pressure range 0 to 12,000 psi. The transducers have certain advantages over those used by King, 1 and the measurement techniques are influenced less by subjective elements than other methods previously reported. An electronic counter-timer having a resolution of 10 nanoseconds measures the transit time of ultrasonic pulses through the sample; elastic wave velocities of most homogeneous materials can be measured with errors of less than 1 percent. 5- and P-wave velocity measurements on Bandera sandstone and Solenholen limestone are reported for the axial pressure range 0 to 6,000 psi and for the uniform pressure range 0 to 10,000 psi. The influence of liquid pore saturants on P- and S-wave velocity is investigated and found to be in broad agreement with Biot&apos;s theory. In specific areas, the measurements do not conform to theory. Velocities of samples measured under axial and uniform loading are compared and, in general, velocities measured under uniform stress are higher than those measured under axial stress. Liquid pore fluids cause increases in Poisson&apos;s ratio and the bulk modulus but reduce the rigidity modulus, Young&apos;s modulus and the bulk compressibility. INTRODUCTION Ultrasonic pulse methods for measuring the shear wave velocity of rock samples in the laboratory have been gradually improved during the last few years. Early experimental pulse techniques reported by Hughes et al.2 and by Gregory 3 were beset by uncertainties in determining the first arrival of the shear wave (S-wave) energy. Much of this ambiguity was caused by the multiple modes propagated by piezoelectric crystals and by boundary conversions in the rock specimens. Shear wave velocity data obtained from the critical angle method, described by Schneider and Burton4 and used later by King and Fate sand by Gregory, 3,6 are of limited accuracy, and interpreting results is too complicated for routine laboratory work. The mode conversion method described by Jamieson and Hoskins7 was recently used by King 1 for measuring the S-wave velocities of dry and liquid-saturated rock samples. Glass-air interfaces acted as mode converters in the apparatus, and much of the compressional (P-wave) energy apparently was eliminated from the desired pure shear mode. A more detailed discussion of the current status of laboratory pulse methods applied to geological specimens is given in a review by Simmons.8 A new shear wave velocity laboratory apparatus has been developed for testing rock samples under elevated pressures. This apparatus employs liquid-solid interfaces as mode converters. The technique for generating pure shear waves at liquid-solid interfaces was developed from studies of critical angle methods.6 Two identical transducers are placed in contact with opposite ends of the rock sample, one transducer acting as an ultrasonic energy emitter or generator and the other acting as an ultrasonic energy receiver or motor. The P-wave energy emitted from the piezoelectric crystal in the generator transducer is converted into pure S-wave energy at the Drakeol-aluminum

By Joseph B. Perry, G. M. Kirwan

MAGNESITE is found in 22 California counties, but many of the deposits are too small or too impure to be of commercial value. Several of substantial size and quality were entirely exhausted by wartime operation. At present, three properties comprise the only known workable deposits in the state. Of these, the Western mine and the Patterson mine have been known and worked for many years, and have been described in considerable detail in various publications, therefore need only brief mention here, because of their proximity to the Bald Eagle mine. The latter, recently developed, is unusual in type of ore deposit, plant design and operation, as well as products made, and very little has been written concerning it. WESTERN MINE The Western mine, 32 miles south of Livermore, Calif., was formerly operated by C. S. Maltby. It has been a consistent producer for many years.1 The ore is of amorphous variety, occurring along fracture zones in serpentine. The veins vary greatly in width, the average being perhaps 8 ft., with the maximum indicated in one early stope of 40 ft.; 2 ft. is considered the minimum for economical mining. The strike of the veins is predominantly north and south, with dip to the west varying from 40º to 75 º. Walls are well defined and as a rule firm and easily supported. Veins range in length from a few hundred feet to 1000 or more. Their maximum vertical extent is about 350 ft., but many run less. Early mining consisted of open-cut and glory-hole work on the larger outcrops. This was followed underground by a modified shrinkage system, the waste and low-grade horses being removed by hand sorting on the tramming levels and transported to surface dumps. Filled-stope mining is used now, in order to eliminate the handling of waste, which has

Jan 1, 1938

By D. Silverman, A. R. Brown

EquipmENT and methods for locating the points of entry of salt water into oil wells are described. These techniques make it possible to delineate accurately the top and bottom boundaries of water zones whether bottom water or intermediate zones of production, Data are given on tests by this survey method on a number of producing wells, Complete results were obtained on wells shelving water percentages ranging from high values to as Little as 10 pct salt water. A number of the wells tested were plugged back and the results are reported in detail. While not all the work-overs were successful, evidence, including the results of reruns by this survey method, points to failure of the plugback operations. The data provided in the tests discussed show, contrary to general opinion, that a large percentage approaching 50 pct of the wells showed intermediate water instead of bottom water. Furthermore, approximately a third of the wells tested showed multiple zones of water production. The equipment comprises a long pipelike assembly carrying 10 pairs of electrodes spaced apart a distance of 4 ft. A surface-controlled solenoid-operated switch is provided to connect each of the individual pairs of electrodes in turn to a single-conductor steel-armored cable by means of which the conductivity of the fluid in the vicinity of each of the electrode pairs can be continuously recorded at the surface. Any number of electrode pairs and any spacing can be used. This assembly is lowered on tubing and placed in position opposite the section of the well to be studied. A conventional rod pump is used to produce the well for the survey. The pump inlet is placed below the lowest electrode pair. The well is conditioned by pumping Out the salt water normally standing in the well and introducing fresh water into the annulus at the surface. When the resistivity of the water standing in the well has been increased to a sufficiently high value, the inflowing fresh water is stopped and the drawdown operation of the survey is started. As the fluid head is lowered by pumping, fluids flow into the well and the entry Of salt water is indicated by the change in resistivity of the fresh water opposite the &apos;Ones Of water entry, The process can be repeated as Often as necessary with little effort and without moving any well equipment to be sure that the fluids produced from each zone are representative Of the true reservoir content. Introduction The oil industry has been concerned from its inception with the control of fluids entering its wells. In order to effect the greatest economy of operation and to get the greatest total production of petroleum liquids out of the ground, the flow of gas and water must be controlled and often extensive workovers are planned and carried Out for this purpose. This has become even more important in recent Years because of the need for the conservation of natural resources. Whereas producing operations concerned with the original completion of a well are assisted to a great extent by a wide variety of instruments developed and perfected for that purpose, workover operations on oil wells have been greatly hindered by a lack of suitable instrumentation. The industry has searched for many years for a satisfactory instrument and process that

Jan 1, 1948

By John R. Green

ROTARY kilns, varying in construction, are used in a variety of processes. Products differ and operating conditions vary according to economic requirements. All of these variables influence the degree of instrumentation and type of control necessary or profitable to install. Products fired in rotary kilns are the results of combined temperature and time treatment and the interrelation of these two factors should be kept constantly in mind in the perusal of this paper. MEASUREMENTS OF KILN TEMPERATURE The securing of proper temperatures within the rotary kiln, either of the charge or of the kiln lining in the high fire zone, are basic objectives of kiln operation; therefore the measurement of these high-temperature conditions merits first consideration. For these measurements, radiation pyrometers, properly designed and protected, have proved adequate, particularly where records or automatic control are desired, while optical pyrometers may serve as portable indicators. Light-sensitive devices or photoelectric cells in this service are capable of producing records as well as certain forms of automatic control. High-temperature measuring devices for rotary-kiln work should have the measuring unit protected from dust, as a continued accumulation of deposit would lower the readings. Fig. I shows a typical application of radiation equipment to a rotary kiln, mounted far enough away from the sighting hole through the kiln hood to be protected from puffs or stingouts and with a sighting tube having a series of settling chambers, to prevent dust from reaching the lens. Although dust conditions inside the kiln itself usually fluctuate considerably and have their effect upon the readings at that moment, such effects are not cumulative and show as a continuous fluctuation in the temperature indicated, provided the radiation unit and recorder are responsive to such slight and rapid temperature fluctuations. The ambient temperature to which a measuring unit is subjected fluctuates from possibly 0° to over 200°F., therefore these changes should have no effect upon the final reading or upon the life of the measuring unit. A very narrow sighting angle is desirable, so that measurement of temperature may be made as far as possible into the high fire zone without effect of the flame temperature. There should be some sighting means on the measuring unit, so that the proper field may be viewed. Measurement of wall temperature taken at a point where the charge has just left the wall is less affected by dusting conditions than when taken elsewhere. Factors Influencing Temperature Table I gives an outline of the factors that produce kiln temperatures and comments on the possibility of measurement and control. Of greater number and of varied influence are the factors that control when, where and how the heat is delivered to the kiln, the type of flame and the rate of

Jan 1, 1941

By Charles Miller

Natural carbon dioxide has recently been exploited in the United States in consequence of oil and gas developments in the Western States and the growing demand by transcontinental and transoceanic shippers for solid carbon dioxide. The discovery by drilling of commercial deposits resulted in consideration of its geographic and geologic distribution and occurrence. Its wide distribution in nature is evidenced by its occurrence in the atmosphere, hydrosphere and lithosphere. The question of origin of carbon dioxide involves consideration of theories similar to those concerning natural hydrocarbons, although available evidence favors an inorganic rather than an organic source. Areas favorable to development of commercial production appear to be those in proximity to igneous rocks or in the vicinity of decadent volcanic activity, where, it has long been known, the gas is evolved either free or dissolved in the waters of fumaroles, geysers or mud pots. Structure contour maps are presented showing the Wagon Mound anticline in New Mcxico and the Farnham anticline, Utah. A well drilled on the latter supplies gas to a 20-ton plant manufacturing solid curbon dioxide at Wellington, Utah, on the Denver and Rio Grande R.R., whence it is shipped to surrounding territory and to the West Coast. Before funds are invested in a plant for the manufacture of liquid or solid carbon dioxide, whether supplied by wells or springs, an effort to ascertain the volume of gas available is advisable. The use of present methods of estimation of gas reserves with modifications to account for the quantity absorbed by any water present in the producing formation is recommended. The Farnham anticline is used as an example and computations are made of the probable volume of gas originally present in the structure. No attempt was made to compute reserves in the Niland area, California, for the reason that in such areas it is believed the volume is indeterminate. Introduction Carbon dioxide, in liquid and solid form, has found a wide variety of uses other than its primary application in carbonating beverages. It is now used in more than 40 different ways, ranging from cooling or freezing to use in gas or liquid form for mechanical purposes, chemical industry, explosive, fire extinction, and tire manufacturing. Undoubtedly the chief supply of carbon dioxide is obtained from industrial plants or artificial sources and until recently natural deposits of the gas have received little consideration. Few will question the utility and perhaps dependability of artificial sources, which possess the advantage over

Jan 1, 1938

By Lester L. Hirst, Henry H. Storch, A. C. Fieldner

Experimental work on liquefaction of coal was taken up by the Bureau of Mines in 1936 when it became evident that a prudent policy from the national point of view should include preparation for the time when gradual exhaustion of petroleum resources would require supplementing the growing demand for motor fuel with gasoline and diesel oil from coal. At that time (1936) certain foreign nations that had no home sources of petroleum, especially Germany, England, and Japan, were conducting active research and at least two of them were producing liquid fuel from coal on a commercial scale. Germany was reported to have an annual producing capacity of 800,000 metric tons of gasoline per year, and England had just put into operation the Billingham plant of Imperial Chemical Industries for the hydrogehation of bituminous coal and tar by the Bergius-I.G. process. The annual capacity of this plant was about 150,000 long tons of gasoline per annum (3500 bbl. per day). With these developments taking place in foreign countries, it seemed important to undertake a long-range program of fundamental research in this country to establish a sound groundwork for the evaluation of foreign work on synthetic liquid fuels and at the same time to obtain data on the oil yields and operating difficulties using various kinds of American coals and lignite to the hydrogenation process. The results of such research would be useful in determining the yields and quality of liquid products obtainable from various coals so that American industry would be in position to select the most suitable coals and make rapid progress in establishing this new industry when the commercial need should arise. It was hoped, also, that progress in a better understanding of the chemistry of coal hydrogenation would reduce the cost of the process materially. To carry out this program, a small continuous unit capable of hydrogenating 100 Ib. of coal in 24 hr. was installed at the Central Experiment Station of the Bureau of Mines at Pittsburgh, Pa. Small steel autoclaves or bombs of 0.3 gal. (1.2 liters) capacity also were used for batch-hydro-genation experiments in the study of the chemical fundamentals of the process. Much valuable assistance was obtained in planning the experimental program and designing the equipment from the Fuel Research Station of Great Britain and the Fuel Laboratories of the Mines Department of Canada, where such investigations had been in progress for several years. Equipment and General Procedure of Research The industrial liquefaction of coal by the Bergius-I.G. hydrogenation process as practiced at Billingham, England, from

Jan 1, 1944

By L. F. Engle, M. A. Hewedi

SUMMARY Initial interest in using solutions of ammonium salts to leach native copper was documented in notes from an AIME meeting in 1871; By 1916-1917, application of the NH3-CO2-H2O system to recover nonferrous metals attained commercial significance, when it was used as a process for copper recovery by Kennecott Copper Corporation and Calumet & Hecla Mining Company. The Caron work in the early 1920s, Freeport Sulphur Company’s achievements leaching Cuban laterites during World War II, out- standing accomplishments in both eastern and western Canada, recovery of manganese related to the work of Dean -- all serve as landmarks as this One Century Review surveys a base for future technology. Current emphasis on compatibility of metals-producing systems with the need to meet environmental protection criteria provides special encouragement to researchers and engineers to find accept- able ways of recovering metals. The ever-present demand of management to design, build and operate facilities on a profitable basis provides additional impetus to apply information from the technical literature to that need. Examination of the general approach to this paper will reveal much that is firm and positive with respect to empirical results -- extractions, recoveries, amenability to familiar proven equipment and materials of construction common to the industry. Although there are many references, there are gaps in the basic scientific data that if filled could lead to even more usefulness; the paper attempts to indicate where further information is needed.

Jan 1, 1973

By T. Federighi, S. Ceresara, C. Panseri

The results of an exploratory investigation by means of resistivity measurements at -195ºC, on the aging characteristics of a set of Al-Mg alloys with a maximum content of 7 pct Mg, are reported. Whereas for dilute alloys (Mg < 1.5 pct) only a decrease in resistivity is observed at about 100°C (due to the elimination of quenched-in vacancies), for more concentrated alloys such a decrease is preceded by an increase in resistivity in the range between -60ºand +40°C. Following some previous suggestions, this increase is considered as good evidence for clustering of solute atoms @reprecipi-tation process). From the analysis of the results it appears that, although the process is substantially similar to that observed in other Al-rich alloys, it is characterized by a strong interaction between vacancies and zones. THE process of formation of Guinier-Preston zones, i.e., preprecipitation,1&apos;2 which occurs during the aging at about room temperature in many supersaturated aluminum-rich alloys, has been extensively investigated in the past few years by several workers.2,3 owever, a very interesting question arises when the case of Al-Mg alloys is considered: although it is very easy to supersaturate Al-Mg alloys, just in the same way as for many other aluminum alloys showing preprecipitation, only very little experimental evidence was available until a short time ago in the literature supporting the existence of "natural" aging in supersaturated Al-Mg alloys (see, for example, Refs. 4 to 6). On the other hand, as is well known, the X-ray method is not useful in this case because the X-ray scattering factors of magnesium and aluminum atoms are about the same. Recently, however, Cordier and Detert7 have stressed that during the aging at about room temperature of a supersaturated Al-Mg 10 pct alloy it is possible to detect an increase in resistivity; since, as is well known, such an increase is observed also in most alloys showing preprecipitation, the above authors have interpreted their results as evidence for the formation of magnesium-rich clusters (or Guinier-Preston zones) during the aging. In the course of or ientative investigations on preprecipitation in several aluminum-rich alloys, we also could detect a similar phenomenon in more dilute Al-Mg alloys, see Instituto Sperimentale Metalli Leggeri, Annual Report, 1959, and also Ref. 8. Since the details of our observations, although of a preliminary nature, differ from those of Cordier and Detert and allow one to draw a more advanced picture of the preprecipitation process in Al-Mg alloys, we have thought it useful to report our results in this paper and to comment on them briefly.

Jan 1, 1963

By J. Downie, H. A. Kendall, G. H. F. Gardner

Some cases of the motion of two miscible fluids in uniform linear models are discussed. There is no bulk flow through the models, and the convection currents are caused solely by density gradients. Horizontal, vertical and inclined positions of the models are treated separately. Analytical formulas for the motion of a narrow transition zone between the fluids are obtained and compared with measurements, and the limitations are discussed. Observations of the ultimate stabilizing effect of diffusion on the motion me compared with the theory. It is shown that fluid motion in an inclined model with a constant rate of bulk flow can be directly deduced from the cases discussed, provided the viscosity ratio is small. INTRODUCTION In some reservoirs, convection currents caused by variations in the fluid densities may be significant. For practical purposes it may be desirable either to minimize the effect, particularly in miscible displacement, or to maximize the effect as in some schemes for the production of heavy crude oils by combustion. Experiments by Craig, et al,l have shown the effectiveness of gravity in reducing the efficiency of a miscible displacement when the mixed zone between the displacing and displaced fluids is narrow compared with the height of the system. The presence of a board transition zone from one fluid to the other has been shown by Perkins, et al,2 to nullify considerably the influence of a difference in density. Indeed, the theoretical discussion given by Perrine3 has shown that when the transition zone exceeds a certain critical length the efficiency approaches 100 per cent. Many additional results 495 have been published on miscible and immiscible displacements which show the importance of density difference and also mobility ratio. The aim of the present paper is to discuss some cases of gravity segregation of miscible fluids in linear models such as are often used in the laboratory to evaluate recovery processes, and to supply additional experimental evidence in support of the conclusions. An attempt is made to calculate simply the magnitude of the fluid motion caused by density pdients and mobility ratios, and to quantify the modifications in the fluid motion produced by the combined effect of molecular and convective dispersion. However, it should be pointed out that the uniform permeability of the models and the use of only a single pair of fluids (whereas several pairs of fluids may be employed in a recovery scheme) severely restricts direct conclusions about natural reservoirs. For conciseness, the motion generated by density gradients is emphasized for the case of no bulk flow through the models. This is not a drastic limitation because, as shown in Appendix A, a fluid motion with a constant bulk flow through any linear model is equivalent to a fluid motion with no bulk flow in the same model inclined at a different angle to the horizontal, provided only that the density is a linear function of the viscosity of the fluid mixture. HORIZONTAL MODEL In this case the model is assumed to have a rectangular cross-section with a horizontal breadth b, vertical height and a great length L. Throughout.the paper it will be assumed that x-axis points along the length, the y-axis along the width and the z-axis along the height. Thus, in the present case the x, y plane is horizontal. Initially, the transition zone between the fluids is assumed to be thin and parallel to the y, z plane. An example of this situation in a practical problem arises in a scheme for using air for cushion gas in the storage of fuel gas in aquifers. 6 With the passage of time the denser fluid sinks and spreads along the bottom of the model while the lighter fluid rises. The interface extends from the top plane of the model to the bottom. Experiments have shown that for practical purposes this interface may be treated as a plane surface at all times. The surface is significantly curved, however, for viscosity ratios greater than about 10. Other complications arise with large viscosity ratios because of the nonlinear dependence of the viscosity on the composition of the mixture, so that the simple results given here are restricted to fairly low viscosity ratios.

By E. H. Jr. Dix

THE work of Merica1 and other investigators indicates that the phenomenon of age-hardening in. alloys of the duralumin type is primarily dependent upon the variation in the solubility of copper with temperature. In addition to copper, however, these alloys contain small amounts of magnesium, silicon, manganese and iron, which may affect the age-hardening either directly or indirectly. The effect of these elements on the solubility of copper and on the manner in which this solubility varies with the temperature is of considerable interest, therefore. The effect of magnesium is of especial interest because apparently it exerts a marked effect on the natural or room-temperature aging of alloys of the type described.2 A series of investigations3 has been in progress in the research laboratories of the Aluminum. Company of America to determine the functions

Jan 1, 1932

By O. N. Carlson, W. M. Paulson

A phase diagram is proposed for the Y-C system based on the vesults of thermal analyses, microscopic obsevvations, and X-ray diffraction studies. Three intermediate phases occur in the system: a congru-ently melting fcc phase with a wide range of homogeneity about the composition Y2C, an intermediate solid-solution region between 55 and 58 at. pct C, and a bct dicarbide melting congruently at 2415°C. All three compounds undergo a phase transformation at elezlated temperatures. A continuous serzes of solzd solutions exists between the fcc phase and the high-temperature form of YC2 with a maximum in the solidus at 2000°C and 30 at. pct C and a minimum at 1805°C and 54 at. pct C. THIS investigation of the Y-C system was undertaken as part of a nuclear materials development program. Yttrium-base alloys are of interest as possible containers for liquid metals, and carbides are currently receiving increased attention as high-temperature materials for advanced reactors and other applications. Previous work on this system was limited in scope, and the results were somewhat inconclusive and at times contradictory. Spedding et al.&apos; reported the existence of a triyttrium carbide having an fcc structure with a wide range of homogeneity and Dean et a1.2 reported the existence of a rhombohedra1 phase having the stoichiometry of Y2C. Bachella et a1.3 observed that the latter was the result of ordering of carbon atoms in the fcc solid solution. The ordering range was placed at 800" to 1000°C. Vickery et a1.4 reported a high-melting compound which they identified as yttrium dicarbide, and Spedding and coworkers1 determined the structure of this phase as bct with lattice parameters a = 3.66 and c = 6.17A. Samsonov et al.5 reported the melting point of YC2 as 2300" * 50°C. Recently Bowman et a1.6 found a transformation in the dicarbide from the tetragonal to an fcc form at 1320 20°C. Samsonov and coworkers7 reported a monocarbide of yttrium melting at 1950" * 20°C and also a sesqui-carbide melting at 1800" * 50°C. The existence of the latter has also been indicated by others,1&apos;8 but neither compound has been definitely established. The Y-C phase diagram shown in Fig. 1 was proposed by Chubb and Keller8 in 1964 based on the data available at that time. The tentative nature of this diagram together with the uncertain status of the compounds indicated that additional work on this system was needed. EXPERIMENTAL PROCEDURE Yttrium metal of 99.9 pct purity was prepared for use in this study by the reduction of YCl, with calcium to form a sponge product.9 The major impurities in this material were as follows: 100 ppm C, 150 pprn H, 20 ppm N, 300 to 1000 ppm O, <20 ppm Ca, <100 ppm Cr, <80 ppm Cu, 150 ppm Fe, <30 pprn Mg, <400 ppm Ta, and <100 ppm Ti. Alloys were prepared by arc melting yttrium sponge together with pieces of high-purity graphite rod in a purified argon atmosphere. Homogeneity was insured by repeated melting, inverting the ingot between melts.

Jan 1, 1969

By B. G. Klugh

The present paper represents a preliminary investigation of the ultimate structure of iron-bearing materials which have been subjected to heat treatment for the purpose of agglomerating the fines, or for chemical changes, or for both. Primarily, the object of this inquiry was to determine the relation of the microstructure of each of these materials to its specific susceptibility to the action in the blast-furnace. It is hoped that this small contribution will serve as a nucleus to a line of research that will throw some light upon the debated questions involved in blast-roasting. Thus far the investigation has been conducted along lines of analogy of known principles, rather than through the application of any well-defined system of microscopic petrography. This is obviously due to the fact that we are dealing with ma-terials which are the artificial products of a new art, rather than with the natural materials from which the essence of the pure science has been evolved. In the limited time allowed for this research, it has been conducted upon those materials the chemical content of which allows of their use commercially in the blast-furnace. The following microphotographs are arranged in the order of the degree of complete fusion to which the mass in question has been subjected, in effectively binding the particles together. A very notable fact here clearly demonstrated is that the degree of fusion to which the material has been subjected is inversely proportional to the reducibility of the product. The characteristic of the material under consideration to which reducibility is almost universally attributed call be progressively traced in the following arrangement, through the identity of the obvious microscopic constituent. Furthermore, the degree of fusion to which a bod? has been subjected is recorded in the presence of resultant products of fusion in that body. Such readjustment is generally apparent

Jan 1, 1914

By Harry M. Bendler, W. A. Wood

Electron metallography has been applied to the study of the torsional fatigue of polycrystalline OFHC* copper. The development of slip bands, fis- sures, and microcracks has been followed as a function of strain amplitude and number of cycles. Those factors that have been found to be relevant to a geometrical theory of the fatigue process are described. From the point of view of this theory it is important to distinguish between the effects of cycling at large amplitudes and at small amplitudes (true fatigue deformation). EARLY investigations showed metal fatigue cracking is caused by continued reversal of a small plastic strain. Fundamental study of fatigue, therefore, has been largely concerned with the cumulative effects of these plastic reversals on the metal structure. In particular, recent work has shown that the plastic reversals produce slip movements that are finer than the slip movements produced by unidirectional increments of plastic strain; individual slip movements in fatigue, for instance, are too fine to see by optical microscopy.2 It has also been shown that the fine slip movements of fatigue tend to concentrate in bands and that in this way they can build up, after enough cycles, a progressive surface disturbance. It is this disturbance which, in effect, makes the slip movement visible. It is also in this disturbance that the first cracks appear to form. From this point of view, therefore, the problem of fatigue becomes one of finding why the fine slip movements should concentrate in bands and why the. bands should finally open into cracks. Thus far, study of the slip bands has been limited to the changes they produce at the surface only. These studies have given interesting results. Ewing and Humfrey3 many years ago showed that the bands in iron could extrude debris. Forsyth found that bands in aluminum alloys could extrude thin tongues of material. Thompson showed that, after lightly dissolving away the surface of copper specimens, some bands persisted as superficial cracks might, and that the life of a specimen under fatigue deformation might be prolonged by dissolving away the surface at intervals. Thus these and related results have suggested that the metal structure in fatigue bands may disintegrate and that this may happen long before obvious cracking. These surface studies, however, have not shown definitely how cracking may begin, for they do not show sufficiently what is happening in depth. However, some advance in this direction has been made recently by a new approach, summarized later, which reveals slip bands and their surface disturbances in section. In the work done thus far, the sections have been studied by optical microscopy only. In the present work they have also been studied by electron microscopy with extended results. This paper also describes some observations on the surface disturbances prior to sectioning. These observations are relevant to a suggested theory of fatigue cracking. REVERSED SLIP MOVEMENTS Slip movements in fatigue deformation must reverse direction in each cycle. The question arises: DO the "backward" and "forward" movements take

Jan 1, 1962