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By Edward J. Felten

Binary Cr-A1 alloys containing from 2.5 to 30 wt pct Al and 0.7 wt pct Y were heated in oxygen, air, and nitrogen between 1000" and 1200°C. The reacLivity of the alloys was found to be dependent both on the alloy composition nnd the nature of t he atmosphere. In oxygen, nllojs containing up to 15 to 20 wt pct A1 reacted to produce an external scale of Crz03 and a subscale consisting Predominently of Al203. Alloys contazning 20 to 30 wt pct A1 react in oxygen to produce an A1203 external scale and little m no subscale. The latter alloys were markedly more oxidation resistant than those of low alurninum content. In air, the alloys on which an external Crz03 scale was formed were found to be permeable to nitrogen ns evidenced by the copious amomts of chromium and aluminum nilrides observed ns part of the subscale. The reactizities in nir (or nitrogen) of these alloys increase <m their aluminurn contents increase. However, alloys on which Al,O, us an external scale is formed were nol culnerable to nccelerated attack in air, and no eltldence of nitvide subscnles were observed. For all alloys, yttrium serwed pYimarily to improve oxide adhrence. THE role of chromium in the oxidation resistance of Fe-Cr alloys &apos;-&apos; and that of aluminum in Fe-Cr-A1 al10s&apos; has received considerable attention in recent years. This is understandable since many of these alloys have excellent oxidation resistance due to the formation of either a Cr203 or a-Ala03 film between the metal and the oxidizing atmosphere. Small additions of yttrium or other rare earth metals are effective in preventing spalling of the protective oxide from the metal substrate."" In contrast, little is known regarding the oxidation resistance of Cr-A1 alloys, although some work has been done by Tumarov et a1.&apos; The poor niechanical properties exhibited by Cr-A1 alloys make them undesirable for use as structural components, but their use as coatings cannot be disregarded. The use of chromium-rich aluminide coatings for refractory metal alloys is an example of the potential use of this type of sytem. The purpose of this work is to examine the oxidation behavior of Cr-A1 alloys containing 2.5 to 30 wt pct A1 and 0.7 wt pct Y. The effects of temperature, atmosphere, and thermal cycling have been determined. EXPERIMENTAL PROCEDURE The alloys used in this investigation can be divided into two groups. Those containing 2.5, 5, 7.5, and 10 wt pct A1 and 0.7 wt pct Y were extensively evaluated in the temperature range from 1000" to 1200°C. Alloys containing 15, 20, 25, and 30 wt pct A1 and 0.7 wt pct Y were tested only at 1200°C. All of the alloys were prepared by standard arc-melting techniques in the form of cylinders approximately 4 in. long and 19 in. in diam. Wafers were cut from the cylinders and subsequently subdivided into rectangular coupons. The alloys were brittle and therefore some cracks were found in almost all specimens. The coupons were prepared for oxidation by mechanically polishing through 600 grit Sic paper, and were thoroughly degreased just prior to testing. Two types of oxidation experiments were conducted, namely; cyclic tests in which the specimens were examined and weighed after each 2 hr exposure, and continuous thermal balance tests run in a controlled atmosphere (oxygen, air, or nitrogen) for 20 hr. In the former test the spalled oxide was not included when the specimens were weighed. The physical condition of a specimen was noted visually after each cycle and testing was continued either to failure or until the performance of the specimen was well characterized. Both Micro and Semi-Micro Thermal Balances (Ains-worth) were used in the continuous tests. The oxidized specimens were sectioned and prepared for metal log raphic examination. The specimens were polished through 600 grit Sic paper. After polishing through 6 and l p diamond, a final mechanical polish with Linde B-Alz03 was used. Specimens containing 2.5 pct A1 were etched electrolytically using a 10 pct oxalic acid solution at 4 v for about 2 sec. Selected specimens were examined in the electron microprobe analyzer. Oxide specimens were examined by standard X-ray diffraction techniques. EXPERIMENTAL RESULTS For convenience, the test results have been broken down according to the exposure temperature, and further subdivided according to the type of test and atmosphere employed. Because of the poor quality of the specimens a larger than normal amount of scatter was observed in the measured rate constants. Also, the evaluation of the weight gain data was done on a somewhat arbitrary basis and may not be truly representative. However, the results obtained do show a significant trend in behavior regarding both alloy composition and the nature of the oxidizing atmosphere. I) Oxidation Behavior at 1000°C. A) Continuous Oxidation estsin Oxygen. This series of experiments was run in the Ainsworth Micro-Thermal Balance using pure oxygen at a pressure of 76 mm Hg. Under these conditions all specimens oxidized in accordance with the parabolic rate law over a major portion of the exposure time; the rate constants appear in Table I. The oxide formed externally on all specimens was predominantly Cr,O,, which was generally adherent. In some cases a slight amount of spalling in the form of a fine powder was noted. a-A1203 was observed as a subscale, along with Yz03 in all alloys. Alloys containing up to 7.5 wt pct A1 oxidize more rapidly than the Cr-0.7Y alloy.

Jan 1, 1970

By J. R. Elenbaas, J. A. Vary, D. L. Katz

The development of gas fields, oil fields and aquifers for storing natural gas is treated from two main vieu.-points: (I) the volumetric storage capacity for gas in a given situation and (2) the prediction of the number of wells required for the delivery of gas. Other experiences in the design and operation of storagc fields are incluclerl INTRODUC TION Storage of natural gas in underground reservoirs near the terminus of long distance pipelines has been the prime factor in opening the space heating market to the natural gas industry. Storagc has permitted a major. increase in both the load and the load factor of pipe-lines; some are now operating at steady load throughout the year. Thus, underground storage has been responsible for the rapid increase in demand for natural gas in recent years. Three types of reservoirs have been used for gas storage: natural gas reservoirs, oil reservoirs, and waterbearing sands or aquifers. This paper presents the factors to be considered when developing gas storage reservoirs of these three categories. There are two prime considerations tor any storage reservoir: (1) the volume of gas which a given reservoir will store advantageously and (2) the number 01 wells needed to provide the required peak deliverability. These two problems will be considered for the three types of reservoirs just noted STORAGE IN PARTIALLY DEPLETED GAS FIELDS Early storage operations consisted of replenishing the natural gas in a depleted gas field situated adjacent to the market. Today, newly discovered fields near the market may be considered for storage, and this discussion applies equally to both types of reservoirs. For reservoirs originally containing gas or oil, the question of the impermeability of the cap rock nor-mally does not arise. However, such fields are likely to have many wells drilled either to or through the reservoir under consideration. Positive assurance must be obtained that such wells are or can be made mechanically tight. Corroded casings may need to be lined or permanently plugged. Abandoned wells should bc reopened and properly cemented. The volumetric capacity for gas storage depends upon space available in the porous rock as well as pressure and temperature of the gas in the reservoir. The production-pressure decline data on partially depleted gas reservoirs without water drive permit calculation of the reservoir space for gas. Isopachous maps of sand volume and porosity data for the reservoir rock provide an alternate method of calculating the pore volume for water-drive reservoirs. The pressure range selected for the storage cycle depends upon ()) the safe upper limit of pressure. 2) the flow capacity of wells and (3) compression requirements when injecting gas into the reservoir or delivering to market. Normally, gas and oil fields have pressures at discovery in the range of 0.43 to 0.52 psi/ft of depth. Pressures of around 1.0 to 1.2 psi/ft of depth appear to lift the overburden1-3 and invite uncontrolled movement of fluids in the porous rock. Some top pressure is normally selected for a storage reservoir ranging from below discovery pressure for deeper reservoirs to 0.65 psi/ft of depth for shallower reservoirs. Pressures to 0.66 psi/ft have been experienced without difficulty. The lower pressure limit is set by water intrusion accompanying low pressures, reduced flow capacity for wells at lower pressures and compression requirements. Depletion-type gas reservoirs often encounter water problems in the later stages of gas production. Such water intrusion may be due to movement from the surrounding aquifer. Accordingly, displacement of this water back into the aquifer by gas pressure and subsequent surges of water corresponding to the gas storage pressure cycle must be considered. Storage fields often produce in four months a volume of gas equal to its initial content. Rapid decreases in reservoir pressure occur, such as 20 psi/day. Accordingly, closed-in pressure observation wells which reflect the pressure in the bulk of the reservoir are required for following the operation of the reservoir. It has been found that a plot of observation wellhead pressures against gas content, Fig. 1, is very useful in observing operation of the field, checking the inventory and predicting future behavior. The plot is based on a given quantity of base or cushion gas in place. The injection and withdrawal curves may spread depending upon the homogeneity of the reservoir rock. permeability of the rock, well spacing and flow rates.

By C. V. Corless

WE are living at a period of the world&apos;s history in which social phenomena are on so vast a scale, are of so profoundly soul-searching a nature, and are occurring in such rapid succession in the great world drama in which we are both actors and spectators, that, in our efforts to obtain a rational point of view in relation to them, our minds may fail to discern the simple in the complex and our understanding is liable to be-come confused or even overwhelmed. To the social student whose scientific training has convinced him of the truth of the evolutionary law, Natura non facit saltum, it is neither the vast scale of the events; their deeply soul-stirring nature, nor their rapid succession that matters so much, as the discovery of the underlying principle or law in accordance with which the disintegration and reintegration, which are the two aspects of social evolution, or indeed of evolution everywhere, are occurring. He is most deeply concerned in seeking an answer to the question: Have we in the present great and perplexing upheavals in human society, whether regarded in Central Europe, in Russia, in Great Britain, or in America, a really new cause at work, or, have we, though on a very- large scale, merely new manifestations of the working out of an old principle? When we think of the appalling struggle in Europe, into which the world&apos;s greatest exemplar of democracy was finally drawn, no one has any hesitation in admitting that the great conflict was fundamentally a life-and-death struggle for self-preservation and self-propagation on the part of autocracy. The variations we meet with in the statement of the cause of the war arise mainly from differing distances of perspective: but in the last analysis all agree that the autocratic system of political government, which found its very soul and center in Prussian despotism, was consciously arrayed in a final "world-power-or-downfall" struggle against a love of freedom which was steadily widening and-deepening throughout the world, and particularly throughout those parts of the world where this love of freedom and justice has found expression in democratic institutions. It is not irrelevant to our discussion to recall in passing that this most imposing structure ever conceived by the human mind as an instrument of tyranny is lying today an irretrievable mass of ruins, completely over-

Jan 4, 1919

Discussion of the paper of George C. Stone, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2401 to 2402. D. S. JACOBUS,* New York, N. Y.:-The engineers of the country are waking up to the possibilities of waste-heat boilers. As the cost of fuel increases, and as more attention is given to economies, it is evident that a great deal may lie gained by utilizing heat that has ordinarily been wasted. The art in the manufacture of&apos; waste-heat boilers has. advanced so that it will now pay to install them under certain conditions where it would not have paid to install boilers constructed in accordance with older methods. In using boilers where the gases are at a comparatively low temperature, a great deal depends on the method of baffling the boiler in securing good results. The Babcock & Wilcox Co. has made a careful investigation of the laws of heat transfer and has applied the same to waste-heat boilers, which have been carefully tested under operating conditions, with the result that we now know what to expect with different arrangements of baffles and heating surfaces. The old idea of installing waste-heat boilers was to provide an arrangement where the draft loss would be a minimum, and little or no attention was paid to the effect of different systems of baffling on the steaming capacity of the boiler. In some instances, to secure a minimum draft loss no baffles were placed in the boilers. After making a most careful study of the subject it developed that this practice was bad, and that to obtain the best commercial economy, in place of endeavoring to obtain a minimum draft loss, an arrangement should be used that would lead to the maximum amount of heat transmission with a comparatively high draft loss. In nearly every case the amount of resistance of the gases fussing through the boiler involves the use of an induced-draft ,fan, but the additional capacity developed by the boiler over that which could be secured with the older designs, through arranging the heating surface properly and using proper baffles, much more than pays for the increase in the steam required to drive the fan.

Jan 12, 1913

By S. H. Lorain, Norman L. Wimmler, S. Ricker, P. E. Oscarson, H. G. Iverson

This paper has been prepared with the principal objective of recording the results of the Bureau of Mines exploration of five major clay deposits in the Western Region. It is based mainly on data contained in unpublished Bureau of Mines reports. Acknowledgment is made to the Federal Geological Survey for its cooperative work with the Bureau of Mines, to the various State geological and mining departments, and other State and local agencies. Clay Exploration by the Bureau of Mines Much has been written and published on clays and clay deposits relating to their refractory, ceramic, and other qualities but such literature is lacking in analyses of the available alumina content of the clays and provides little indication of their possibilities as a source of alumina. With this new objective in view, a great many of the known clay deposits were reexamined and new ones discovered. The Bureau of Mines made preliminary examination of numerous areas in the western United States. Five of those most favorably indicated were systematically drilled, and in each a large amount of high-alumina clay has been found. These five major projects are Molalla and Hobart Butte, in western Oregon; Cowlitz-Castle Rock, in southwestern Washington; Ione, in California; and the Olson-Troy area in Idaho (Fig. I). Preliminary scout drilling was done in the Stockton deposit at Coeur d&apos;Alene, Idaho; the White ware deposit near Lewis-town, Mont.; and 13 areas in the Spokane or eastern Washington region, where the most favorably indicated area, known as the Excelsior, is now being drilled more systematically. Preliminary drilling was undertaken in numerous areas adjacent to the major deposits and others more remote. As a result, large additional clay possibilities were found. The Clay Deposits The clay deposits under consideration are of the sedimentary or transported types, parts of which have been altered further by the agencies of weathering, ground water, or hydrothermal action. There are extensive deposits of residual clays in northern Idaho and in eastern Washington, but they have been found to be low in the available alumina and to contain much free quartz, mica, and unaltered feldspar. To be of value, they must first be subjected to beneficiation to remove these gangue minerals. The sedimentary clays have been derived largely from the decomposition, erosion, and transportation of granites, gneisses, schists, and basalts. At Molalla, some

Jan 1, 1948

By Norman L. Wimmler, H. G. Iverson, S. Ricker, P. E. Oscarson, S. H. Lorain

This paper has been prepared with the principal objective of recording the results of the Bureau of Mines exploration of five major clay deposits in the Western Region. It is based mainly on data contained in unpublished Bureau of Mines reports. Acknowledgment is made to the Federal Geological Survey for its cooperative work with the Bureau of Mines, to the various State geological and mining departments, and other State and local agencies. Clay Exploration by the Bureau of Mines Much has been written and published on clays and clay deposits relating to their refractory, ceramic, and other qualities but such literature is lacking in analyses of the available alumina content of the clays and provides little indication of their possibilities as a source of alumina. With this new objective in view, a great many of the known clay deposits were reexamined and new ones discovered. The Bureau of Mines made preliminary examination of numerous areas in the western United States. Five of those most favorably indicated were systematically drilled, and in each a large amount of high-alumina clay has been found. These five major projects are Molalla and Hobart Butte, in western Oregon; Cowlitz-Castle Rock, in southwestern Washington; Ione, in California; and the Olson-Troy area in Idaho (Fig. I). Preliminary scout drilling was done in the Stockton deposit at Coeur d&apos;Alene, Idaho; the White ware deposit near Lewis-town, Mont.; and 13 areas in the Spokane or eastern Washington region, where the most favorably indicated area, known as the Excelsior, is now being drilled more systematically. Preliminary drilling was undertaken in numerous areas adjacent to the major deposits and others more remote. As a result, large additional clay possibilities were found. The Clay Deposits The clay deposits under consideration are of the sedimentary or transported types, parts of which have been altered further by the agencies of weathering, ground water, or hydrothermal action. There are extensive deposits of residual clays in northern Idaho and in eastern Washington, but they have been found to be low in the available alumina and to contain much free quartz, mica, and unaltered feldspar. To be of value, they must first be subjected to beneficiation to remove these gangue minerals. The sedimentary clays have been derived largely from the decomposition, erosion, and transportation of granites, gneisses, schists, and basalts. At Molalla, some

Jan 1, 1948

By F. A. Hames, D. S. Eppelsheimer

The ferromagnetic copper-manganese-aluminum and copper-manganese-tin alloys (Heusler alloys) owe their ferromagnetism to the beta phases (body-centered cubic structure) in their respective systems.l,2,3 The ternary beta phase regions in these systems are extensions of the beta fields of the binary copper-aluminum and copper-tin systems into the ternary models of the copper-manganese-aluminum and copper-manganese-tin systems respectively. X ray analysis has indicated the presence of long-range order in the more strongly magnetic alloys.3,4,5 The ideal ordered structure is obtained in alloys of compositions Cu2MnAl and Cu2MnSn; the copper atoms occupy positions at cube centers while the aluminum (tin) and manganese atoms alternate at cube corners. This atomic arrangement is illustrated in Fig 1. The compositions Cu2MnAl and Cu2MnSn are also those that show maximum magnetic saturation moment. 3,4,6,7 Departures from these compositions result in a decrease in the degree of order attainable and a decrease in magnetic saturation moment. In view of the chemical similarities of aluminum, tin, indium, and gallium, and the existence of beta phases in the binary systems copper-indium and copper-gallium, it may be suspected that ternary beta phases exist in the systems copper-manganese-indium and copper-manganese-gallium, and that these are ferromagnetic. The purpose of this investigation was to determine whether ferromagnetic beta phases exist in the systems copper-manganese-indium and copper-manganese-gallium analogous to the ferromagnetic beta phases in the systems copper-manganese-aluminum and copper-manganese-tin. Previous Work At the time this investigation was started no information could be found regarding the constitution of copper-manganese-indium and copper-manganese-gallium alloys, nor of the binary manganese-indium and man-

Jan 1, 1950

By E. O. Kirkendall

The investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,l particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize: it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosen-hain,2,3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,&apos; and Johnson8 all proposed theories to explain diffusion. Langmuir&apos;s proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,1 and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. Experimental Procedure This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ± 3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 1/4 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photomicrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 1/2 hr. at 300°C. It was then etched in 25

Jan 1, 1942

By E. O. Kirkendall

The investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,l particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize: it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosen-hain,2,3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,&apos; and Johnson8 all proposed theories to explain diffusion. Langmuir&apos;s proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,1 and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. Experimental Procedure This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ± 3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 1/4 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photomicrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 1/2 hr. at 300°C. It was then etched in 25

Jan 1, 1942

By John Mullen

Impingers TWO types of midget impinger apparatus are used at Climax. The Mine Safety Appliances Company&apos;s midget impinger (MSA) and the Climax Molybdenum Company&apos;s midget impinger (CMC) (Fig. I). The Leiman Brother&apos;s No. 25, positive displacement pump is used in the CMC impinger instead of the four-cylinder radial pump that is used in the MSA impinger. With the MSA apparatus it is possible to obtain the proper vacuum by adjusting the needle valve on the vacuum chamber, while with the CMC impinger the proper vacuum is obtained by varying the rate at which the pump is cranked. The Leiman Brother&apos;s No. 25 pump is built to displace 0.1 cu. ft. of air per min. when operated at 145 r.p.m. In the CMC impinger this pump is so geared that the required crank speed is approximately 59 r.p.m. Both types of impinger apparatus are equipped with a water gauge mounted on top of the case and they are calibrated and operated in reference to the gauge. The MSA impinger flasks and nozzles are used with both types. Calibrating Impingers A calibrated precision Sargent wet-test meter (Fig. 2) is used in calibrating the impinger apparatus. The apparatus is set up as for taking a sample in the field, except that the hose from the outlet side of the meter is attached to the impinger nozzle. One revolution of the large hand of the meter indicates 0.1 cu. ft. of air displaced. The impinger pump is cranked for one minute, therefore, at a rate that will cause the large hand of the meter to make one revolution. The gauge reading is noted, then the impinger is cranked at this rate for 10 min. and is checked for error. If the meter indicates that more or less than I cu. ft. of air has been displaced, the impinger must be cranked—ither slower or faster according to the error—for another 10 min. and again checked for error. This operation is repeated until the proper gauge reading for a sampling rate of 0.1 cu. ft. per min. has been determined. This gauge reading is used in all sampling operations until the impinger is again calibrated. An impinger is calibrated at least twice each week. MlCROPROJECTOR A Bausch and Lomb model B micro-projector is used (Fig. 3). It consists of a substantial metal base supporting the light source and a microscope. Illumination is provided by a Bausch and Lomb 4.5-amp. arc lamp with mechanical feed. A glass water cell filled with a heat-absorbing and color-filter solution is placed between the arc lamp and the microscope. Two types of solution have been found satisfactory— a 2 per cent solution of copper sulphate or a 2 per cent solution of picric acid and distilled water. This percentage may be varied to give the desired color to the light reflected upon the screen. Any standard microscope may be used. A Bausch and Lomb microscope with

Jan 1, 1946

By Donald B. Evans, Robert D. Pehlke

The solubility of nilrogen in liquid binary alloys of iron with Litanium. zivconium, columbium, vanndiurn, and tantalum was measured for alloy composiLions up to the solalbility limils of lhe alloy nitrides. All five alloying agents were found to decrease markedly the activity coefficient of nitrogen in liquid ivon. The metal/nitvogen mole ralios in the alloy nitrides formed were generally .found to be slighlly greater than 1.0, but in no case greater than 1.5. From the experimental data, the standard free energies of fortmation of titanium and zir-conium nitrides have been calculated for the Lemperaluve range 1550° to 1750 C. The solublily Products for columbium, tantalum, and vanadium nitrides are also reported. A number of research investigations have examined the effect of refractory metals on the solubility of nitrogen in liquid iron. Although data on zirconium are not available, investigators are in agreement that titanium, vanadium, columbium, and tantalum markedly increase the solubility of nitrogen in liquid iron. This fact alone makes desirable the acquisition of thermodynamic data for these elements in liquid iron. Since refractory metals are known to be stable nitride formers, they have been suggested as steel denitrifying agents, and some of their nitrides have recently been considered as containment materials for liquid iron and iron alloys. Most available thermodynamic data for these metals relate to their dilute concentrations, but effective thermodynamic treatment of these applications requires data at concentrations near the solubility limit of the alloy nitride. Although some work has been done at relatively high alloy concentrations in liquid iron (particularly for vanadium 2,3 and titanium 2,4), the results have been somewhat contradictory. Disagreement may be partly attributed to the fact that the compositions of most refractory metal nitrides have been shown to be nonstoichiometric, and to vary 2,5-8 depending on the temperature and nitrogen gas pressure with which the solid nitride phase is in equilibrium. One purpose of this study consequently has been to determine the compositions of the refractory metal nitrides precipitated from a liquid iron solution. EXPERIMENTAL PROCEDURE Rao and Parlee2 and Evans and Pehlke 9 have discussed the technique for measuring the solubility product of an alloy nitride phase in liquid iron by finding the point of departure of the nitrogen solubility from Sieverts&apos; law. The method consists of measuring the solubility of nitrogen in a melt of iron containing a known concentration of a second metal as a function of the nitrogen gas pressure over the melt. In this study the second metal was one of the refractory metals titanium, zirconium, columbium, vanadium, or tantalum. When the nitrogen pressure at which the refractory nitride forms is reached, a deviation of the measured solubility of nitrogen in the melt from Sieverts&apos; law is observed in the form of a "pressure halt." The concentration of nitrogen in the melt associated with this breakpoint in the nitrogen-absorption curve is then used to calculate the nitride solubility. The Sieverts method was used to measure nitrogen solubility as a function of nitrogen pressure and temperature. The experimental equipment for this technique has been previously described in detail. 1,9 Charge materials used were vacuum-melted high-purity iron (Ferrovac-E) and the best commercial grades of the refractory metals obtainable (in all cases at least 99.8+ pct pure). Recrystallized alumina crucibles were used to hold all melts except those containing zirconium, for which zirconia crucibles were necessary. Temperatures were measured by a disappearing-filament type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diameter sight hole in the crucible lid. By means of a technique previously described, 9 in which the refractory-metal nitride was precipitated at one temperature then redis-solved by raising the temperature 50°C and precipitated again at a higher temperature, it was possible to obtain data over a temperature range of up to 200°C on a single melt. It was found that this technique could not be used with melts containing zir-

Jan 1, 1965

By H. F. Ramstad, F. D. Richardson

The equilibria (a) SiOz +Hz =SiO +H20 and (b) Si + SiO, = 2Si0 have beet1 studied at temperatures of 1425"to 1600°C ad 1310°to 1485°C respectively. The stattdard free energy changes for the tzrro reactions are given by the equatiotts Combination of the results for both equilibria leads to tiotz removes certain anomalies in existing high-terlzperature data for equilibria involving silica and silicon in iron. In many metallurgical processes and in many laboratory investigations silicon monoxide undoubtedly plays an important role. It is unfortunate therefore that wide differences exist between the results obtained by different investigators1-7 in their studies of such equilibria as In an attempt to put our knowledge of SiO on a surer basis, an exhaustive study has been made of equilibria [I] and [2] at temperatures ranging from 1300" to 1600°C. Reaction [I] was studied by measuring the amounts of silica which could be condensed from streams of Hz or Hz + HzO which had previously been brought into equilibrium with silica at temperatures ranging from 1425" to 1600°C. Reaction [2] was studied by measuring the material that could be condensed from streams of Hz or argon which had been brought into equilibrium with mixtures of silicon and silica at temperatures ranging from 1310" to 1485°C. EXPERIMENTAL Materials. The silicon was "superpure" grade and contained less than 0.1 pct impurities. The silica was prepared from pure mineral quartz; this was crushed and treated with concentrated hydrochloric acid to remove particles of iron, washed with water, and finally dried at 120°C. For the hydrogen + silica reaction, the silica was sized to —20+100 mesh. For the silicon + silica reaction, the two materials were ground to a fine powder in an agate mortar. The hydrogen and argon were commercial oxygen-free gases. The gas streams were controlled with capillary flow meters and the volumes were measured by wet gas meters. After passing through the meters, the gases were partially dried by silica gel. The hydrogen for the HZ + SiOz reaction was then passed through palladised asbestos at 300°C and dried with magnesium perchlorate. The efficiency of oxygen removal was checked throughout the experiments by passing the gas over an electrically heated strip of nichrome, used as an indicator as described by Rathman and de itt.&apos; When mixtures of HZ + Hz0 were required, the partial pressures of water vapor (1.8 to 22 mm) were obtained by passing the hydrogen through oxalic acid dihydrateg&apos; lo held at various controlled temperatures, O.l°C, by means of a water bath. The hydrogen for the Si + Si02 reaction was purified by passing it over a mixture of 3 parts of magnesium to 5 of lime heated to 600°."l1 u The argon for this reaction was passed through titanium powder (-3/16 in. + 100 mesh) heated to 900°C. The nitrogen used to prevent the reaction products escaping from the condenser (see later), was deoxidized by copper or iron at 600°C. All these gases were finally dried with magnesium perchlorate. Furnace, Temperature Contr01, and Measurement A molybdenum resistance furnace was used for both sets of experiments. The reactions were conducted inside a high-grade alumina tube, 36 in. long and 1 in. in diam as indicated in Fig. 1. With this arrangement an even temperature zone (2"C) 4 cm long was satisfactorily obtained. The temperatures were kept constant by means of a proportional controller actuated by a Pt-Pt 13 pct Rh thermocouple. This was placed between the two alumina tubes, so that the temperature at the junction was 1400" to 1450°C. Up to 1485"C, the temperatures were measured with Pt-Pt 13 pct Rh thermocouples. For higher temperatures an optical pyrometer was used, this being sighted (through the glass window 1 in Fig. 1) on the end of the alumina tube, that held the SiOz or Si +SiOz mixture, 10 in Fig. 1. The optical pyrometer was recalibrated whenever a change was made in any part of the apparatus situated in the hot zone. Successive readings with the optical pyrometer were reproducible to within 1"C. Equilibrium Apparatus and Procedure. Hydvogen and Silica Reaction. The apparatus is shown in Fig.

Jan 1, 1962

By J. H. Swisher

In measuvements of the solubility of nitrogen in fer-rilic Fe-P alloys, tile nitrogen solubility is found to be Less in pIrospliorus-bearing alloys than in pure iron. The reduction in solubility is about 20 pct in a 1.0 wt pct P alloy at 1300°C and about 30 pct in a 0.23 wt pct P alloy at 440°C. Diffusion coefficient measurements at 1150 and 585°C show that phosphorus also decreases the nitrogen diffusivity in iron. In previous work on the Fe-P-N system, phosphorus was found to reduce the nitrogen solubility in liquid iron slightly.&apos; Indirect evidence for similar behavior in a Fe at low temperature was obtained by Dickenscheid and Brauner.&apos; These authors found that phosphorus reduces the height of the internal-friction peak due to dissolved nitrogen. The results of Dickenscheid and Brauner were confirmed by J. C. Swartz of this Laboratory in a single internal-friction experiment using the same specimen stock as in the solubility measurements described below. In the present investigation, the solubility of nitrogen in a fer rite-stabilized Fe-1.0 wt pct P alloy was measured in the temperature range from 800" to 1300°C. Additional experiments were performed in the temperature range from 440° to 585°C, using an Fe-0.23 wt pct P alloy and NH3-H2 gas mixtures. EXPERIMENTAL The experiments were performed in a vertical tube furnace wound with platinum wire. For experimental temperatures of 800°C and above, a mixture of 5 pct Hz in N2 was used as the reacting gas. The gas mixture was prepurified from oxygen by passage over platinized asbestos at 450°C, and subsequently over anhydrone to remove water. Flow rates of the gases were measured with capillary flow meters. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. The specimens used for the high-temperature solubility measurements were in the form of rectangular plates, 0.534 by 1.6 by 3.8 cm. The specimens were cleaned in trichloroethylene and annealed for 2 hr in hydrogen at the beginning of each experiment. In measuring the nitrogen solubility, the specimens were held in the reacting gas until equilibrated, then cooled in a water-cooled copper block at the bottom of the furnace. The time needed for equilibration at 1150°C was determined by measuring the average nitrogen content of the 1.0 pct P alloy as a function of reaction time. As will be described, the nitrogen diffusivity in the alloy at 1150°C is only slightly less than its calculated diffusivity in pure iron. At temperatures other than 1150°C, the reaction time used in measuring the nitrogen solubility was about twice the calculated equilibration time for pure iron at the same temperature. With a few exceptions, the procedure for the low-temperature solubility measurements was the same as that described above. The compositions of the NH3-H2 gas mixtures were determined by collecting gas samples from the gas train and analyzing them for NH3 by titration with HC1. The specimen thicknesses were less than those used for the high-temperature experiments, eg., 0.124 and 0.051 cm for measurements at 585° and 440°C, respectively. Nitrogen concentrations were obtained by chemical analysis, using the Kjeldahl method. The Fe-P alloys were made by adding ferrophos-phorus to electrolytic Plastiron (Type 104 A). Commercial ferrophosphorus, containing 3 pct Mn and 0.35 pct Si as the major impurities, was first purified by melting under an FeO slag. In a separate heat, the electrolytic iron was melted and vacuum-carbon-deoxidized prior to making the ferrophosphorus addition. The principal impurities and their concentrations in weight percent in the 1.0 pct P alloy are as follows: Mn, 0.01; Si, <0.01; C, 0.01; 0, 0.003; and N, 0.0012. The impurity levels in the 0.23 pct P alloy are con-

Jan 1, 1968

By T. N. Singh, B. Singh

SUMMARY. The supports account for over 501 of the total expenditure for a longwall face. The success and economics of a face depend upon the optimum selection of type and density of the supports. Empirical solutions involving uncertain safety factor are replaced by a geo-mining approach developed at OMRS in which the support resistance is defined by the stability index of the roof rock mass and the failure pattern of the immediate roof. The paper gives the methodology adopted to define the support resistance for Alkusha colliery longwall face of Jharia coalfield (India). The stability index of the roof mass varied from 218 to 520 for the individual beds and 1100 to 1374 for the immediate roof mass. The exact support resistance for the condition was found to be 42 t/m2.

Jan 1, 1982

Discussion of the paper of W. C. PHALEN, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 93, September, 1914, pp. 2249 to 2265. DAVID T. DAY, Washington, D. C.-Consider the United States broadly and the distribution of the salt industry. Think of the old solar-evaporation process up in New York State, then of the more recent processes in Michigan and Kansas and Louisiana, where the rock salt furnishes a large industry, then of the solar-evaporation process at Salt Lake, then turn to the crucial place in the United States, where there is an embarrassment of salt, and that is California. I am not forgetting&apos; the immense body of salt east of that in the Virgin River country of Utah; but in California the situation is interesting. There are very large quantities of salt in the Searles Marsh region; again, in Southern California, at the southern end of Death Valley, there are two or three mountains of salt which have been explored recently, where the salt is sufficiently pure to be used at once. There is also a large deposit of gypsum, and it would be possible there, by extremely cheap means, to produce an amount of salt sufficient to furnish the United States&apos; greatest needs. The principal reason that capital has been deterred from developing such a large mass is not the fact that solar evaporation produces a great deal of salt around San Francisco, but the fact that if potash salt is to be produced in connection with the salt in the borax region a, great deal of ordinary salt must be disposed of. It cannot be dumped, for it would get back into the brine again; the first rains would bring that salt back into solution again. It must be sold, given away, or hauled to a distance, which would mean a considerable freight charge. The salt will be going begging. E. G. SPILSBURY, New York, N. Y.-The remark of Dr. Day&apos;s regarding the likelihood of the production of a large amount of waste salt brings to my mind the condition that obtains in Germany in all of the potash fields. In Germany salt is a government monopoly. In the development of the potash deposits, it becomes a grave question as to how much salt they may be allowed to extract and bring to the surface.

Jan 4, 1915

By N. A. Gokcen, R. A. Dodd

Solubility of nitrogen in liquid iron-manganese system at 1550°C and one atmosphere pressure has been determined by a simple method. Results show that the solubility increases from 0.040 pct for pure iron to 1.41 pct for pure manganese. DETERMINATION of the solubility of gases in volatile metals. and alloys by the well-known Sievertsl method is unreliable. This is particularly true for the Fe-Mn system since Mn vaporizes readily from the alloys containing as little as 2 pct Mn, and, upon condensing on the cooler parts of the apparatus, it absorbs large amounts of nitrogen. Further, the condensing Mn vapor interferes with the usual method of temperature measurements with an optical pyrometer.

Jan 1, 1962

By John Chipman

Published data on the equilibria of carbon in binary Fe-C austenite with H2-CH4 and CO2-CO gas mixtures are used to obtain the constants of an equation repre -senting the activity coefficient of carbon throughout the stable austenite range of temperatutre mid compositiotl. Calculated values for the solubility of graphite are found to be in agreement with the best-published direct observations. Its heat of solution is 10,680 calper g-atom. The free energy of formation of cementite is culculated from the equilibrium compositions of austenite and of gas. Its entropy and heat of formation are also obtained. BASIC knowledge of the high-temperature properties and treatment of steels is contained in the Fe-C diagram and its extensions for the effects of alloying elements. The application of thermodynamics to the Fe-C system, with addition of alloying elements, can serve to simplify and systematize this knowledge. The points of beginning are the binary fee solution, austenite, concerning which our information is reasonably complete, and the binary carbide, cementite. Further studies must include the other phases of the binary system, a and liquid, and for these an accurate knowledge of the ? phase boundaries is essential. These studies should provide a firm base for systematic study of the effects of alloying elements on all phases of the system, their transformations, and precipitation phenomena. With the aid of the simplifying thermodynamic concepts of activity coefficients and interaction parameters it is to be hoped that the results of these studies will be amenable to computer solution thus making the information on multicomponent systems more readily available than would be possible in multidimensional diagrams. Studies of the thermodynamic properties of austenite have utilized equilibrium measurements on the reactions:

Jan 1, 1968

By John W. Chang

Introduction Automatic control of primary ball mill circuits has received much attention over the past decade, primarily because its advantages ultimately can be translated into economic terms. Apart from such obvious benefits as improved product quality, increased throughput, and more stable operation, less direct benefits such as easier operation, more orderly maintenance scheduling, and timely management reports all can be realized with the application of modern automatic process control equipment and techniques. Software configurable digital computer-based control systems offer ease of change in control strategies. Occasional control strategy changes are necessary whenever control objectives change or circuit modifications occur. The dependency of control strategies on control objectives and circuit equipment to effect optimal circuit operation is an important, but often neglected issue. Because of the potential for even better control, research and development work continues. [See (Ulsoy & Sastry, 1981) and (Hulbert & Braae, 1981).] Some of the possibilities are discussed later in this presentation. A few preliminary remarks may be in order concerning the relationships among control objectives, control strategies, and circuit equipment. Generally accepted control objectives for primary ball mill circuits include: 1. Maintaining a desired percent solids in the mill. 2. Maintaining a desired measure of particle size distribution at the cyclone overflow. 3. Maximizing throughput. Control Objective I is a requirement for proper operation of the ball mill, especially if it is a grate mill. It concerns smooth movement of material through the mill. Control Objective 2 is a product specification - one of the requirements for proper flotation operation. Control Objective 3, an expression of the desire to get the most out of the circuit, is the easiest to evaluate in economic terms. It assumes that the processes downstream

Jan 1, 1982

By B. T. Brady

Rock mechanics, like all engineering disciplines, must have a theoretical foundation. The subject of this chapter is the formulation of analytical methods that may aid in the rational design and determination of the stability of engineering structures in competent brittle rock materials. By an engineering structure in rock, we mean any (1) excavated sub- surface opening, (2) open surface structure, or (3) system of openings in rock that is virtually self-supporting-that is, not requiring artificial systems to carry structural stresses. One factor necessary for designing or evaluating a structure&apos;s stability is knowledge of the material&apos;s mechanical properties, such as stress-strain behavior and fracturing characteristics. The composition of most structural materials such as metals and concrete is uniform and reproducible to the degree that their mechanical properties in service are nearly the same as those measured in the laboratory. Consequently, a rational design can be made on the basis of published mechanical property values. The same equivalence does not exist for rock materials for two reasons: (1) the composition of even the most common rock types is highly variable, and (2) the problem of the size effect is present. Mechanical property tests not conducted at a scale that includes these effects in normal proportion will not be representive of the in-situ rock mass. Of course, the alternative is to perform the test in-situ. Comparatively few mechanical property tests have been performed in-situ because of the physical limitations of test equipment and the prohibitive cost. The current procedure is to design a structure based on small-scale laboratory measurements, with a safety factor usually determined by the experience of the design engineer. While this procedure is somewhat unsatisfactory, laboratory measurements can and do provide a useful basis for the initial design.

Jan 1, 1970

By M. E. Wadsworth, D. R. Wadia

The rate of reaction of cuprite was measured in a series of sulphuric acid solutions, from which oxygen had been excluded, at various concentrations and temperatures. The overall reaction CuzO + H2S04 + Cu " + CuO + H20 + So4&apos; may be explained quantitatively by two simultaneous rate reactions involving not only H+ but also the hydrolytic adsorption of H2SO4. The results indicate the importance of considering surface mass balance relationships associated with heterogeneous surface reactions. T EACHING has long been an important method for the recovery of metals from certain minerals. Many processes have assumed minor importance in modern practice but such operations as the recovery of uranium and present interest in high pressure-high temperature solution of sulphides&apos; &apos; well illustrate the importance of leaching as a unit operation. Little quantitative information is available in a form sufficient to determine the mechanism of solution at the solid-aqueous solution interface for given systems. For this reason, it is important that fundamental studies of leaching processes be conducted so that parameters associated with such surface reactions may be understood and correlated. Cuprite was chosen for this study as a result of a recent investigation carried out at the University of Utah on ores of the Ray and Chino Mines Divs. of the Kennecott Copper Corp. These sulphide deposits contain sufficient oxidized minerals, such as cuprite, malachite, and azurite, so that recovery of metal values contained in the oxidized fraction is of primary interest. Of these oxides, cuprite (Cu,O) is the most interesting, since it dissolves in sulphuric acid by an oxidation reduction couple resulting in the formation of 50 pct metallic Cu and 50 pct cup-

Jan 1, 1956