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By Richard S. McCaffery, Joseph F. Oesterele

This investigation was undertaken to determine the quality of different iron blast-furnace slags as desulfurizing agents, and the possibility of using, in the blast furnace, materials of higher sulfur content than is now common. The solution of the problem would render possible the use of higher sulfur iron ores for pig iron and cokes containing more sulfur than now employed, and the economic manufacture of irons and steels of lower sulfur content. It is generally assumed that the sulfur that reaches the lower part of the iron blast furnace is removed from the pig iron by combining with lime to form calcium sulfide. Most of the sulfur introduced with the charge is in combination with iron or manganese or, perhaps in the coke, as a carbon compound.1 The iron and manganese sulfides are more soluble in the iron than is calcium sulfide, and as the latter is generally said to to be more soluble in the slag than the iron and manganese sulfides, this greater solubility of calcium sulfide in the slag tends to free the metal from sulfur. This greater solubility of the calcium sulfide is used not only to reduce the sulfur contents of the pig iron in the blast furnace, but by this means also low-sulfur steels are produced in the open-hearth and electric furnaces. The reaction2 FeS + CaO + CO = Fe + CaS + CO2 requires a high temperature and strongly reducing conditions in the presence of lime. The constitution of blast-furnace slags, first studied scientifically by Vogt13 indicated certain ranges of composition of the slag in which a

Jan 1, 1923

By Clemens Jones

A FORM of apparatus for volumetric determinations which shall possess the features requisite for the constant use of potassium permanganate, is a very desirable fixture in a well-appointed laboratory. Expedients to economize time and insure accuracy are generously employed for various other reagents, while the permanganate seems to have been consigned to the use of an ordinary burette, and a black bottle of the standardized solution. But the introduction of new, methods dependent on the permanganate, and the urgency of technical requirements where it has long been indispensable, require a revision of practice more scientific and convenient. The apparatus designed by the writer for the laboratory of the Thomas Iron Company at Hokendauqua, Pa., is so simply contrived and works with such entire satisfaction that a description of it may be of use. It may be prefaced that the characteristics of a suitable device offer some mechanical difficulties when combined in a continuous appliance. The burette, B (50 C.C. to 1/10 c.c.), shown in Fig. 1, consists of the graduated tube proper and an arm, E, fused to it below the 50 c.c. mark. At its top are rubber connections with the blast-aspirator, shown in the cut (Fig. 2) of the front view. By means of an extra stopcock, D, connection through E is established with the reservoir F. The burette is clamped Securely to a slide, C, which is counterpoised and moves freely on guides between two parallel sides, L, suitably

Jan 1, 1887

By Henry G. Petrow, Edward S. Porter

MAJOR occurrences of lignite with significant uranium concentrations have been reported in western parts of the Dakotas, especially in Harding County, S.D., and Billings and Slope counties, N.D. Samples containing as much as 2 pct U3O8 were received at the Winchester Laboratory, but those deposits reportedly of major significance have generally contained 2 to 4 lb of uranium per ton of lignite. Most of the uranium appears to be associated with the carbon in the lignite as a urano-organic complex, although in most instances analysis of inorganic material has shown uranium values. Molybdenum is similarly associated with the carbon, and its concentrations generally parallel the uranium. The noncarboniferous material is mainly composed of gypsum, jarosite, bentonite, sandstone, and miscellaneous carbonates and silicates. The heating value of these lignites has been determined as about 3500 Btu on a dry lignite basis. The ash content of lignite has varied widely, the important samples containing 30 to 60 pct ash on a dry lignite basis. Because of the significant upgrading of uranium values obtained by ashing the lignite, and because recovery of uranium from raw lignite presented formidable processing problems, major emphasis at Winchester has been placed on devising methods to recover uranium from lignite calcines. Proper roasting removes the problem of organic fouling of solutions, reduces the size of the leaching plant for an equivalent uranium throughout, and generally provides equal or better acid leaching efficiency with less acid than can be obtained from the raw lignite.

Jan 9, 1957

By Thomas C. Wilder, Walter E. Galin

Measurements of the electromotive force of the cell at 995°C have shown that the cell may be used to detennine the zinc content of molten Cu-Zn alloys to the nearest 0.05 wt pct. The cell is used for brass melts to which no ZnO is added intentionally, because essentially all oxygen in the Cu-Zn-O system is present in the form of ZnO. The cell is also used to detev,nine the thernodynamic activity of zinc for Cu-Zn al1oys of the brass composition range, from which the equilibrium partial pressure of zinc for such alloy may also be calculated. The electrochemical measurement of the concentration of the most active metal in other engneering- alloy systems by a similar technique is also considered. IN recent years there have been many studies concerning the direct electrochemical measurement of oxygen content in molten engineering metals.' These investigations employ galvanic cells in which the electrolytes are various solid mixed-oxides which conduct current by movement of oxide ion vacancies under the influence of an oxygen potential gradient. Similar cells have also been used to measure the thermodynamic properties of mixing of solid alloys,' one component of which has a much greater affinity for oxygen than the other component(s). One alloy system of obvious engineering importance comprised of two metals of greatly differing affinity for oxygen is copper-zinc. At the casting temperature of molten brasses, the zinc concentration is very difficult to control not only because its vapor pressure is very high, but also because of its high affinity for oxygen to form ZnO. Inasmuch as brass castings may be required to have a zinc concentration within very narrow limits, it would be advantageous for the brass industry to have a means for quickly measuring the zinc content in the molten alloy just prior to pouring. A calculation based on earlier thermodynamic studies of oxygen and zinc in dilute solution in binary Cu-O and CU-Z' alloys indicates that the oxygen concentration of molten 70 wt pct Cu-30 wt pct Zn brass must be much less than 1 ppm for the separate phase ZnO not to exist in the ternary Cu-Zn-O system. Thus it can be assumed that all molten brasses, both in the laboratory and in the foundry, are sufficiently saturated with oxygen for the separate phase ZnO to be present. In view of the foregoing reasons, the cell investigated at 995°C for the purpose of measuring the zinc concentration in molten copper-zinc alloys, particularly those of brass compositions. In this cell the left hand electrode is a reference electrode comprised of a mixture of the pure powders of nickel and nickel oxide, to which a platinum contact is made. The electrode of interest is a molten Cu-Zn alloy of unknown zinc concentration with a tantalum wire contact. The electrolyte is the commercially available (Zircoa) calcia stabilized zirconia. The ZnO in the Cu-Zn electrode compartment is not intentionally added, but is naturally present as a result of the infinitesimal amount of oxygen required for its formation in this alloy system. In cell [A] nickel oxide is reduced at the cathode where O= represents the electrolyte. At the anode dissolved zinc of the Cu-Zn alloy is oxidized to form ZnO(s) in its standard state Thus the overall reaction is for which the molar free energy change is where 5 is the Faraday equivalent (23,063 cal per v equivalent), is the electromotive force of the cell in volts after correction for the Pt-Ta thermocouple, FOf (ZO) and AFF (NO) are the standard molar free energies of formation of the respective oxides, and a2n is the thermodynamic activity of zinc in the molten Cu-Zn alloy. The reference state of zinc in this case is taken to be the pure liquid. At constant temperature all the terms of Eq. [I] are constant except and azn Thus since all other participants in the electrochemical reaction are in their standard states, the change in the electromotive force of Cell [A] is represented only by a change of the thermodynamic activity of zinc at constant temperature. The zinc concentration is related to the activity by sampling the alloy for chemical analysis after cell measurements are taken. EXPERIMENTAL A typical cell construction is shown in Fig. 1. This and other experimental details were similar to that described earlier with the exception of some minor modifications which are detailed below.

Jan 1, 1970

By F. O. Willhofft

The symposium on mine safety held in connection with the annual meeting of the Institute three years ago, it. was pointed out that "at present no convenient, reliable, accurate means for determining the gas content of mine air is available, for use by the ordinary mine man." In a letter addressed to Coal Age and published on Feb. 25, 1925, Thomas T. Read, then Director of the Safety Service of the Bureau of Mines, stated: "It is to be hoped that sometime in the near future some-one will invent a reliable methane indicator that is con-venient to, use and will permit the keeping of all flames of every character out of bituminous mines, through doing away with the safety lamp." The Martienssen methane detector, which has re-cently received the official approval of the Bureau of Mines, is intended to. meet the demand for such an in-strument as expressed at that meeting and on many other occasions. The characteristics which qualify it for the task are the following: (1) simplicity; (2) small bulk and light weight; (3) ruggedness; (4) accuracy sufficient for the requirements; (5) safety; and (6) dependability. The principle on which the working of the instrument is based may best be explained by giving a brief out-line of the various stages of development through which the inventor, Professor Martienssen of the University of Kiel, Germany, advanced to the final solution of the problem which he had undertaken to solve.

Jan 2, 1928

By C. Gatlin, F. Armstrong, K. E. Gray

This paper presents some preliminary results of two-dimensional cutting tests of dry limestone samples at utmospheric pressure. Cutting tips having rake angles of + 30°, + 15", 0°, - 15" and - 30" were used to make cuts on Leuders limestone samples at six depths of cut ranging from .005 to ,060 in. at cutting speeds of 15, 50, 109 and 150 ft/min. The vertical and horizontal force components on the cutting tips were recorded with an oscilloscope equipped with a polaroid camera. Motion pictures of the cutting process at camera speeds of 5,000 to 8,000 frames/sec were taken at strategic points in the variable ranges. The movies provide considerable insight into the brittle failure mechanism in rocks. It appears that chip-generating cracks usually have an initial orientation which is related to the resultant of the externally applied forces. The latter part of the crack curves upward toward the free surface being cut, this part being governed by some type of cantilever bending or prying. The linear and angular motion of the loosened chips also indicate the tensile nature of brittle failure. Analyses of the forces on the cutting tips indicate that: (I) relatively small increases in vertical loading result in large cut-depth increases for sharp tips (rake angles 2 0"); (2) tool forces increase at an increasing rate as the rake angle decreases, particularly for rake angles < 0"; and (3), for the range of this study, rate of loading had little effect on the maximum forces. Both the movies and visual inspection of the cuttings indicated that the volume of rock removed by chipping was much larger than that by any grinding mechanism, even for tips having negative rake angles. Cutting size increases with increased cut depth and rake angles, and decreases slightly at high cutting speeds, the depth of cut having by far the most influence. The amount of contact between the rock and the cutting tip was always less than the depth of cut and rarely exceeded 0.010 in. even for cuts of 0.060 in. INTRODUCTION The planing (or slicing) of various materials with a fixed blade has long been practiced by workers in many industries. For example, the farmer&apos;s plow, the carpenter&apos;s plane and the housewife&apos;s paring knife all employ this basic action. The casual observer might suspect that something so common must be quite simple; however, as in all problems involving the failure of materials, such is not the case. Industries concerned with the machining of metals have long studied these problems, and their literature on the subject is voluminous. Despite these efforts, basic knowledge is not very advanced, as may be noted from recent and comprehensive analyses of their literature.12 Metals are more subject to analysis by classical theories of elasticity and/or plasticity than are rocks, since their elastic constants and strengths are reasonably well established in many cases. In spite of this relative "simplicity", Hill9 refaces his discussion with an admission that the mathematical solution to the machining problem is not known. Photoelastic studies of both machining and milling have been performed and are discussed thoroughly by Coker and Filon.4 Rotary drilling of rocks with fixed blade or drag bits has long been practiced by the mining and petroleum industries, and considerable study has been given to defining their cutting action in terms of the pertinent variables. Essentially all the published mechanistic research on drag-bit drilling has been performed by mining engineers and has been concerned only with rocks in the brittle state. Fairhurst5-7 has worked extensively in this area and employed photographic techniques quite similar to those reported here, except at much lower speeds. His studies showed the periodic or cyclical nature of the brittle failure mechanism, in which instantaneous loads on the bit varied from some maximum value to near zero. Goodrichs has presented further data on the subject as well as a qualitative description of the process. Again the postulated mechanism is cyclical, with alternate chipping and grinding periods. The ploughing of coal is a practiced method and has been studied in some detail by English mining engineers."" Their findings have considerable general application to drag-bit drilling. Evans," in particular, has extended Merchant&apos;s metal-cutting theory" to brittle materials with some success, although certain aspects of his theory are open to question. Fish13 has recently summarized nearly all the published works concern-

By G. Bhat, J. F. Libsch

A STUDY of the kinetics of embrittlement in engineering alloy steels during tempering has indicated that the presence of alloying elements may define two distinct regions of embrittlement: 1) at 800° to 1000 °F, termed low temperature embrittle-ment, and 2) in the temperature range 1150 ° to 1250°F, termed high temperature embrittlement.13 It has been suggested that embrittlement in each region may be due to a different mechanism. At intermediate temperatures and extended times the course of embrittlement may be influenced by the superposition of the embrittlement occurring in the two regions. Furthermore, low temperature embrittlement has been known to decrease as the temperature is raised slightly above the maximum embrittlement range.&apos; Jaffe and BuffumV ave presented data for a Ni-Cr steel illustrating the removal of the em-brittlement occurring at 932°F by reheating to 1250°F for an hour. Their data further shows that embrittlement proceeds continuously with increased time at 1250°F, becoming pronounced at long times. They interpreted this behavior as a retrogression phenomenon involving the solution of the small nuclei of precipitate formed at 932°F as the temperature was increased, and reprecipitation of larger nuclei stable at 1250°F, with the reoccurrence of embrittlement. It appears desirable to reconsider this explanation in the light of the two regions of embrittlement proposed by the authors1 for some alloy steels. In addition, it appears desirable to determine any influence of a preconditioning treatment in each temperature range upon subsequent development of low and high temperature embrittlement. It is thus the object of this investigation to study the characteristics of the two modes of embrittlement proposed in a commercial Ni-Cr alloy steel (AISI 3140). Experimental Details Material—The material used in this investigation was commercial AISI 3140 steel bar stock, received as % in. hot-rolled rounds. The steel analysis was as follows (in percentages): C, 0.39; Mn, 0.79; Si, 0.30; S, 0.028; P, 0.015; Ni, 1.26; and Cr, 0.77. Material Processing and Heat Treatment—The bar stock was first ground to 0.430 in. squares and cut into specimens 23/4 in. long. These specimens were austenitized at 1650°F for 1 hr and oil

Jan 1, 1958

By Nicholas T. Camicia

A career in the coal mining industry today offers students one of the most interesting and challenging opportunities available in the industrialized world. As reserves of other fossil fuels dwindle in face of the world&apos;s demand for energy, it has become apparent that coal, once the king of energy sources, must be relied upon again as the major fuel for powering industrial growth in developed and developing nations. Centuries of coal supplies lie beneath the earth&apos;s surface, assuring the world of a steady, plentiful supply of energy until science and technology can produce a way to harness and efficiently use renewable sources, such as solar. The need to increase our use of coal during the last two decades of the 20th century is reason enough to believe that the future growth of the coal industry is assured. A major impediment to that growth might be backward national public policies that could restrict the full utilization of our coal reserves. These policies could result from overregulation and a failure of the public to recognize that coal use, with proper techno- logical safeguards, is compatible with our society&apos;s environmental-quality objectives. Communication of this problem and its solution is a major undertaking of the coal industry in the 1980s. At the end of the 1970s, the American coal industry was producing approximately 635 Mt/a (700 million stpy) of coal. To meet the nation&apos;s projected energy needs by 1985, the annual tonnage must be doubled. A similar scenario is predicted for the rest of the world. Such growth in the modern international business world will require huge additional amounts of capital, equipment, and people who know how to wisely raise and apply the capital; use the equipment productively; and deal with the many community, public, and governmental problems such expansion will create. Whether a student&apos;s interest is in actual mining operations, business administration, engineering, finance, law, industrial relations, marketing

Jan 1, 1981

By Nicholas T. Camicia

A career in the coal mining industry today offers students one of the most interesting and challenging opportunities available in the industrialized world. As reserves of other fossil fuels dwindle in face of the world&apos;s demand for energy, it has become apparent that coal, once the king of energy sources, must be relied upon again as the major fuel for powering industrial growth in developed and developing nations. Centuries of coal supplies lie beneath the earth&apos;s surface, assuring the world of a steady, plentiful supply of energy until science and technology can produce a way to harness and efficiently use renewable sources, such as solar. The need to increase our use of coal during the last two decades of the 20th century is reason enough to believe that the future growth of the coal industry is assured. A major impediment to that growth might be backward national public policies that could restrict the full utilization of our coal reserves. These policies could result from overregulation and a failure of the public to recognize that coal use, with proper techno- logical safeguards, is compatible with our society&apos;s environmental-quality objectives. Communication of this problem and its solution is a major undertaking of the coal industry in the 1980s. At the end of the 1970s7 the American coal industry was producing approximately 635 Mt/a (700 million stpy) of coal. To meet the nation&apos;s projected energy needs by 1985, the annual tonnage must be doubled. A similar scenario is predicted for the rest of the world. Such growth in the modern international business world will require huge additional amounts of capital, equipment, and people who know how to wisely raise and apply the capital; use the equipment productively; and deal with the many community, public, and governmental problems such expansion will create. Whether a student&apos;s interest is in actual mining operations, business administration, engineering, finance, law, industrial relations, marketing

Jan 1, 1981

By W. A. Backofen, R. L. Fleischer

Single crystal, bicrystal, and polycrystal tensile tests of aluminum at 4.2°K, 77°K, and 300°K have been used to examine the role of grain boundaries in the deformation process. Results indicate that a grain boundary may affect the extent and slope of easy glide. The stage II hardening rate, on the other hand, is independent of the presence or absence of grain boundaries. This conclusion allows the size of the region of multiple slip caused by an incompatible grain boundary to be determined. For the size of bicyystal sample used in this study, multiple slip occurs in about half of the cross section. PREVIOUS studies of the stress-strain characteristics of bicrystals of face-centered-cubic metals have been limited to aluminuml-5 at room temperature. Recent results, however, indicate that the stress-strain curves of single crystals of such metals may be separated into at least three stages6 in which different deformation processes are occurring7 provided testing is done at sufficiently low temperatures.&apos; Since for aluminum a well-defined stage II develops only below room temperature, previous studies have not been able to relate effects of grain boundaries to all of the three stages of deformation. It is therefore to be expected that low-temperature deformation of aluminum single crystals and bicrystals should clarify the effects of grain boundaries on the different processes of deformation. EXPERIMENTAL PROCEDURE Single crystals and bicrystals were grown from the melt by the standard techniqueg with aluminum reported by Alcoa to be 99.993 pct pure. Ridges in the boat were used to guide the grain boundary during growth, assuring that the boundary would bisect the sample.10 The rate of furnace motion during growth was 1.0 cm per hr. During growth zone purification resulted, as evidenced by the ability of the first material to freeze to recrystallize at room temperature following severe deformation. Samples were approximately 4.4 X 6.6 mm in cross section and 103.5 mm in length between grips. Samples were annealed at 635" i 5°C for 40 hr and furnace cooled over a 7-hr period. They were then electropolished in a solution of 5 parts methanol to 1 part perchloric acid at a current density of 15 amp per sq dm for about 30 min at temperatures below 0°C. Tensile testing was performed at 295" (room temperature), 77" (sample in liquid nitrogen), and 4.2"K (sample in liquid helium) on the hard-type machine indicated schematically in Fig. 1. The machine con- sists basically of a tube surrounding a rod; one end of the sample is attached to each member, and the rod is pulled up the tube to extend the sample. The rod is rigidly mounted and is moved vertically by a system described by asinski." The pulling force is measured continuously by an electrical strain gage load cell, and the relative displacement of the tube and rod is also recorded continuously by a soft cantilever beam with electrical strain gages. Maximum stress and strain sensitivities were ±2g per sq mm and * 3-10-5. In all tests the strain rate was approximately 5.10-5 per sec. The thin wires in the tensile apparatus introduce softness, which may be corrected for, however, by measuring load vs displacement with the sample replaced by an elastic member. For loads greater than 15 kg the spring constant is 1.875.106 g per cm. The flexible wires also served to reduce substantially the large shearing forces which may arise in the case of grips having horizontal rigidity.&apos;&apos; As in any gripping system, however, bending moments will arise in the course of deformation by single slip. Engineering stress, s = (load)/(original cross-sectional area), and strain, E = (increase in length)/ (original length), are used for stress-strain curves unless otherwise indicated. Tables list resolved shear stress, T=mo and shear strain ? = dm, where m is the usual Schmid resolved shear stress factor for the primary slip system at the start of deformation. The first group of samples to be described forms an isoaxial set, all of the crystals making up the single crystals or bicrystals having the same tensile axis, the orientation of which is indicated by the cross in Fig. 2. For this orientation the primary slip plane and slip direction make angles of 45 deg with the tensile axis and the Schmid factor m has its maximum possible value of 0.5. Rotations about the tensile axis are indexed by means of an angle 0 between the small-area surface of the samples and the projection of the primary slip direction onto the cross section, as defined in Fig. 3. In single crystals, values of 0 were 0 and 90 deg, while in bicrystals 0 values were (0 deg, 180 deg), (90 deg, 270 deg), and (0 deg, 90 deg) as indicated in Fig. 4.

Jan 1, 1961

El Indio, eighty percent -owned by Compania Minera an Jose Inc., a subsidiary of St. Joe Minerals, and twenty percent-owned by private Chilean investors, will open their new flotation and Carbon -In -Pulp plant near La Serena, 480 km (300 miles) north of Santiago, Chile, in early 1981. The underground mine, at an altitude of 4,270 m (14,000 ft), will produce about 1,270 mt per day (1,400 st per day) of ore containing about 2. 2570 Cu, and gold and silver to the extent of 16 and 254 g per mt (0.47 and 7.4 oz per st) respectively. While construction of the plant was underway, development ore, containing some 1,400 kg (45,000 oz) of gold, was shipped to the United States for recovery in a copper smelter. At El Indio the underground ore is rail-hauled to the mill a short distance from the portal where it is crushed, ground, and floated to produce a copper concentrate containing both gold and silver. The crushing plant also crushes waste for use as mine backfill. Approximately 92% of the copper and 60% of the gold and silver are recovered in the flotation concentrate. Flotation tailings, at a grade of 19 g Au and 116 g Ag per mt (3.4 oz Au and 0.55 oz Ag per st), are cyanided for 72 hours in six Pachucas with auxiliary air lifts for pulp transfer. Lime, cyanide, lead nitrate, and a phosphate are also fed to the cyanidation Pachucas. After cyanidation, the pulp is treated in four air lift Carbon-In-Pulp tanks equipped with external vibrating screens for carbon advance. Loaded carbon is stripped in two pressure vessels in parallel. Pressure stripping must be used because of the high altitude. Stripped carbon is dewatered in a spiral classifier before being reactivated in a rotary kiln and returned to the C. I. P. circuit. Pregnant solution is then sent to four banks of four Zadra cells for gold and silver recovery on steel wool. Zadra cell cathodes.are washed with the slimes being captured in a plate and frame filter. The filter cake and the washed cathodes are then dried on an infrared dryer and smelted in two stages to bullion bars. Published reports indicate that the total investment for this unique operation was in the neighborhood of $80 million.

Jan 1, 1981

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane&apos; by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By M. G. Corson

THE theory of hardening by interference with slip which has been so clearly developed by Jeffries and his co-workers requires that an alloy to be amenable to age or heat hardening should contain among its components some that will stay in solid solution at high temperatures and precipitate as a secondary phase on cooling. This secondary phase may be either a more or less pure individual element (chromium in the case of copper, anti-mony in the case of lead), or some intermetallic com-pound. Those cases of hardening which depend on the precipitation of a compound are not only the most frequent, but are also far superior in the efficiency of hardening obtained. However, the slip interference theory as stated in its most general form is not sufficient to foretell new cases of this type of hardening and also will not explain some phenomena of a more intricate nature. It is not sufficient that a secondary phase might be absorbed by the main one at high temperatures and precipitated at the lower ones. The kinetics of this precipitation and the accompanying. physical phenomena of dimensional changes play independent and highly important parts. These kinetics, while not yet sufficiently studied to he formulated in the shape of physicochemical equations, might find their expression-in a qualitative systema-tization of the phenomena of precipitation according to two different viewpoints. To begin with, we encounter the question as to the velocities of the precipitation and of the growth of the phase precipitated. To harden a metal in an efficient manner we must be able to control the precipitation on one hand and also to bring the total of the secondary phase to such a number and size of the particles pre-cipitated as, will produce a desirable hardening effect under commercially feasible conditions of. age or heat hardening. From this viewpoint six different cases may be dis-cerned.

Jan 7, 1928

By Carl H. Unruh, D. L. Katz

Experimental data are presented for hydrate formation conditions for gas mixtures of carbon dioxide and methane. Equilibrium constants for carbon dioxide, defined as the mole fraction of carbon dioxide in the gas phase (dry basis) divided by the mole fraction of carhon dioxitle in the hydrate (dry basis)... were calculated usine the equilibrium constants for methane developed in an earlier paper. INTRODUCTION A series of papers have been written on gas hydrates, giving temperatures and pressures at which hydrates would form.2. 3, 4. 5, 6. 9. 12, 13, 15 Vapor-solid equilibrium constants have been developed for methane, ethane, propane and iso-butane&apos; by which it is possible to compute for a specific gas mixture the temperature and pressure at which hydrates will form. Carbon dioxide is present in many natural gases in concentrations usually from 0.1 to 2.0 per cent. It also forms a gas hydrate with water and presumably enters the solid solution when present with a natural gas which is forming a hydrate. The equilibrium constant giving the ratio of the concentration of carbon dioxide in the gas phase to the concentration in the solid phase is required for including the effect of the carbon dioxide when computing the conditions for hydrate formation. Direct determination of the concentration of carbon dioxide in solid hydrate requires a difficult separation to be made. Therefore, this research resorted to the measurement of the temperature and pressure at which specific mixtures of methane and carbon diox- ide would form hydrates. From the equilibrium constants previously mentioned for methane, it is possible to compute the equilibrium constant for carbon dioxide, without measurement of the composition of the solid phase. Fig. 1 shows the conditions at which methane and carbon dioxide form hydrates. The methane curve FG extents to some high pressure while the carbon dioxide curve AB intersects the vapor-liquid water-liquid carbon dioxide

Jan 1, 1949

By John Norton

IN spite of the very general employment of nitride hardening, there is still considerable doubt as to the real nature of the mechanism involved. Experience has shown that the addition of small amounts of hardening elements to iron or steel results in a wide variety of desirable properties in a nitrided case. Perhaps the foremost of these elements is aluminum and in this investigation an attempt has been made to study the behavior of aluminum during the hardening process. It is believed that the establishment of a complete atomic picture of the metal at various stages of the process will indicate the relationships between the several kinds of atoms and their individual influences on the physical properties in a clear and direct fashion. A consideration of the problem suggests a surprising similarity between the mechanisms of nitride hardening and of age-hardening. It is now generally understood that age-hardening may take place by one of two distinct processes, the first involving the precipitation of a finely dispersed phase and the other being concerned with the modifica-tion of an existing phase. Following much the same line of reasoning, two theories of nitride hardening have been suggested. The first expla-nation, which has been generally discussed, particularly by Fry,1 states in brief that the presence of aluminum causes the precipitation of alumi-num nitride during nitriding and that this finely dispersed phase is the primary cause of hardening. The second explanation, which has not been published but which has been freely discussed by those interested in the problem, postulates the substitution of aluminum atoms for certain of the iron atoms in the several iron-nitrogen phases in the same manner that the substitutional iron-aluminum solid solution is formed. The marked increase in hardness, as compared with the aluminum-free

Jan 1, 1934

By B. R. Hollebone

The chemical action of molten anhydrous pyridinium chloride (pyridine hydrochloride) on oxy salts and ores of some Group IV and V metals are discussed-in particular zirconium, hafnium, niobium (columbium) , and tantalum. Laboratory-scale experiments are described whose results suggest that this reaction might provide a practicable means of converting ores of these metals to the anhydrous metal chlorides. Experimental results are given which provide some insight into the nature of the reactions and some of the compounds which could be present at intermediate stages. The treatment of ores of the more refractory metals is difficult and expensive and often demands the use of gaseous chlorine, hydrogen fluoride, or other reagents which are, if nothing else, expensive and dangerous to use. This situation is, of course, due to the strong metal-oxygen affinity resulting from the high charge and the small size of the metal ion which combine to produce such high lattice energy in the metal oxide as to defeat standard reduction methods. Thus, the characteristic of these metals which leads to one of their most important properties—corrosion resistance—is the main hurdle in obtaining the metal. Many common methods&apos; for treating ores of zirconium and niobium (columbium), for example, proceed as directly as possible to the preparation of anhydrous halides. These halides are purified by now standard processes of solvent extraction, fractional distillation, and so on. This paper reports on preliminary stages in the development of a method of treating these ores—particularly of niobium—so as to prepare the anhydrous, volatile halides by the use of chemical reagents which are much more easily handled than those used at present. CHEMICAL PRINCIPLES The solvent action of aminium halides has been referred to periodically in the literature over several decades. The chemistry of pyridinium chloride has been discussed particularly by Audreith2 and Starke.3 However, since this is not familiar chemistry in its nonaqueous setting, it is perhaps well to point out some general metallurgical principles and applications. One can use, as point of departure, the fact that HC1 dissolved in pyridine is an acid very much the same as aqueous HC1. It thus gives essentially all the reactions of the HC1 with which we are familiar. However, when the ratio of HC1:pyridine reaches 1:l (a ratio far higher than is possible with H2O) the solution becomes solid C5F5NHC1, pyridinium chloride.* Inter- estingly, the acidic properties of HC1 persist in this medium, although they are manifest only in the molten state of the compound. Some typical reactions of divalent metal compounds which we have carried out in our laboratories are the following: 2PyHCl + Zn — (ZnCl2) + H2 + 2Py 2PyHCl + MnO — (MnCl2) + H2O + 2Py 2PyHCl + CuS — (CuCl2) + H2S + 2Py 2PyHCl + CaCO3 — (CaCl2) + H2O + CO2 + 2Py In these equations, the parentheses indicate a solvated compound which in water would be predominantly a hydra ted cation but which in molten PyHCl will more likely be a complex chloro-anion of the type MC14-. Some important physical properties of pyridinium chloride (PyHCl) are given in Table I. One sees from the data in Table I that at the temperature of molten pyridinium chloride both water and pyridine will boil away. Thus the system will be kept anhydrous. For this reason the reaction 2NbCl5 + 5H2O— Nb2O5 + 10HC1 has no counterpart in molten PyHCl. Instead, the chloride is made even more stable by the formation of a hexachloro complex: Nb2O5 + 12PyHC1 — 2PyHNbC16 + 5H2O + 10Py One interesting property of these complexes is their thermal instability which for the case of niobium can be illustrated as PyHNbCl6 — PyHCl + NbCl5 With a view to possible use of this chemistry in ore treatment, we have attempted to dissolve Pyrochlore (essentially FeO - Nb2O5) and recover the NbC15 from it.

Jan 1, 1968

ZAY JEFFRIES, Cleveland, Ohio (written discussion?).-The authors conclude that there is a certain average size of precipitated CuAl2 par-ticle which produces maximum strength and hardness in duralumin; that when the size of particle is smaller or larger than this particular size the hardness decreases. The writer agrees with this conclusion, because it seems to he directly indicated by the facts. Why does duralumin present this apparent discrepancy? Let us con-sider some physical aspects of the precipitation of CuAl2 from a saturated solution on cooling. When a molecule of CuAI3 is removed from the solvent, or matrix, and added to another group of CuAl2 molecules, as is known to occur on slow cooling, the forces of adhesion between the CuAl2 molecule and the solvent have been exceeded. Since a. change in tem-perature only is sufficient to cause precipitation, it must also be sufficient to cause the loss of adhesion bonds between the excess CuAl2 molecules and the solvent, or matrix. Lost adhesion bonds means loss of cohesion of the mass as a whole. When duralumin is cooled from 500° in a furnace, globules of CuAl2, large enough to be seen easily with a high-power microscope, are formed. There are, however, globules so small as to be hardly distinguishable, and others too small to be resolved are suggested by the non-uniformity of the surface appearance of the section. As the smallest globule of CuAl2 resolvable with a high-power microscope contains about 2,000,-000,000 molecules, it is evident that with rapid cooling submicroscopic particles of CuAl2 must be present in large numbers; in fact, after quench-

Jan 12, 1919

By R. F. Slack, J. C. Draper, J. A. Younkins

In 1959, the Duquesne Light Co. was faced with the problem of moving more than 40 million tons of bituminous coal in Greene County, Pa. The coal had to travel a distance of about 4 ½ miles from a new mine portal in Rocky Run Valley to the company preparation plant and loading facilities on the Monongahela River. After careful study of this immense transport problem, Duquesne decided that the belt conveyor system described in the following pages offered the best solution. This system, now in operation, is probably one of the four or five longest permanent overland conveyor systems in existence. The general layout of the entire system is shown in Fig. I. A detailed description of the salient features of the system is presented below. THE MINE The valley of Rocky Run where the system begins is very, very narrow and very steep. It was chosen as the site of Duquesne&apos;s new mine portal because it was the only place on this particular property where the Sewickley coal seam cropped out. The valley also had two other advantages. First, it fronted on a state road and, second, it offered a site where some 4 million gallons of water could be stored for use in dust-allaying sprays needed in the mine. The company elected to construct a drift mine in the valley because this would require neither the hoisting time of a shaft mine nor the walking time of a slope mine. As part of the mine construction project, the valley was leveled by relocating its stream and filling its center with material cut from each side.

Jan 11, 1966

By S. R. Zimmerley, John Gross

A survey of the status of ore dressing in 19231 placed particular stress on the need of research in the crushing and grinding of ore, especially on the need for a method of measuring the surface of the products obtained in crushing and grinding and for fundamental data on the law of crushing, in order that intelligent conclusions may be drawn from actual crushing or grinding experiments. There has been no satisfactory means of determining the surface of crushed products. The results have been judged entirely by the amount of the various sizes produced, based on sieve sizing for particles above 74 microns in size and on microscopic measurement or elutriation for particles below 74 microns, a method which could give only a general idea of what had been accomplished. The fact that the long controversy between the followers of Kick and of Rittinger has resulted in no accepted conclusion is evidence of the need for fundamental data on the crushing law. Some Methods of Measuring Surface of Particles A dissolution method was used by Wolff to measure surfaces of glass powder. A mixture of sodium carbonate and sodium hydroxide was the solvent and the amount of glass dissolved in two hours from the powder was compared with that dissolved from a glass plate.2 Lately Herbert F. Kriege has used the dissolution method in determining surface of calcite and limestone.3 Dr. Geoffrey Martin and his coworkers in England have also used a dissolution method to determine surface on quartz. They compared the amount of quartz dissolved from the sample in one hour by a hydrofluoric acid solution with the amount dissolved from a measured quartz

Jan 1, 1930

By J. W. Rutter, K. T. Aust

In previous studies of grain boundary migration in zone-refined lead, the authors used bicrystal specimens consisting of a striated crystal which was grown from the melt, and an adjacent striation-free crystal, introduced by artificial nucleation and growth.1 While this method permits the study of the motion of individual grain boundaries, it does not provide control of the relative orientations of the grains. The present note will describe a technique for controlling the orientations of the two crystals in this type of specimen. The technique consists essentially of placing a striated crystal and a striation-free crystal of controlled orientations end-to-end in a graphite trough, then melting a short zone at the junction of the two crystals and allowing it to freeze to form the desired grain boundary. The apparatus used to carry out this process is illustrated in Fig. 1. It consists of a trough milled from high-purity graphite,with grooves in the underside for the placement of thermocouples. The graphite piece fans out on one end at the level of the bottom of the trough; the sides of the trough are completed in this region by the attachment of a mating plate with a slot cut at any desired angle to permit reorientation of the crystal placed at this end of the assembly. The joint between the crystals is made at or near the point where the slotted plate joins the rest of the trough. The thermocouple slots are deepened in this region so that the thermocouples are separated from the melt by only 1/32 in. of graphite. An induction heater, with suitable temperature control, is used to obtain the molten zone. The two single crystals used are first chemically polished in a solution consisting of eight parts glacial acetic acid and two parts 30 pct hydrogen peroxide. They are then placed in the trough with the ends to be joined at the position of the thermocouples. Next, cooling is applied to the two crystals by means of air

Jan 1, 1962