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By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,' is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors' sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958

By William R. Webster

I have continued the investigation of the Pottstown Iron Com pany's basic Bessemer keel plates on the line referred to in my paper of last October (Trans., xxi., 766)) and have added a study of the hardening effects of sulphur, which were not taken into account at that time. The results are so encouraging that I now give them in full. For some months we have graded all the steel at these works by the table given in my former paper, and checked the grading by the forging-tests as described in the paper of Mr. Joseph Hartshorne, read at the same meeting (Trans., xxi., 748). The steel thus graded was bloomed for the plate orders. Then one slab was rolled into a plate for the order, and a tension-test was made of this plate. By the result of this tension-test we were guided in rolling the balance of the heat. Out of several hundred heats graded in this manner, 95 per cent. met the requirements of the orders in every respect, and were accepted; but these results will no doubt be improved upon, when the influence of sulphur is also considered.. The hardening effect of sulphur seems to be about 500 pounds per each .01 per cent. of increase. In the table accompanying the pres ent paper, the ultimate strength with .06.5 per cent. sulphur agrees with the old table where sulphur was not considered; that is, for all steels with less than .065 per cent. sulphur we now get lower re sults, and for those with more sulphur, higher results. Making this allowance for sulphur, the assumed ultimate strength of a 3/8-inch plate of pure iron is reduced from 38,000 pounds per square inch to 34,750 pounds. With this as a basis, I have constructed my new table, giving each of the elements, carbon, phosphorus and manganese the same hardening effect as before, to wit : Carbon is credited with a constant effect of 800 pounds per each, 0.01 per cent. Phosphorus shows greater effect in high-carbon than in low-carbon steels. For 0.07 and 0.08 C, it has about the same effect as carbon, that is, 800 pounds for each .01 P. This increases to 1500 pounds per .01 P in 0.15 C steel, or nearly twice the effect of carbon. This

Jan 1, 1894

By Joseph A. Norden, A. R. Willson

Much has been written concerning the hoisting equipment of various mines throughout the country, but most of the literature on the subject, if not all, describes equipment of extraordinary capacity and the small and medium-sized outfits have been neglected. The hoisting equipment here described is capable of handling about 1200 tons per day. It has not been worked to capacity, but 600 to 700 tons, together with men and materials, have been handled in two shifts without any great effort. Only one shaft extends from the surface to the lowest levels of the mine; see Fig. I. It is composed of three compartments, two of which are used for hoisting, and the third for water, air, and electrical lines, and for sinking purposes. In 1909, this shaft was raised from the 1000-ft. (304-m.) level to the 700-ft. There a station was cut and an air hoist installed. At this time all mining operations were confined to the upper levels of the mine; that is, above the 700-ft. The ore was dropped to this level through chutes from the 300-, 400-, 500-, and 600-ft. levels and then lowered in cars on cages to the 1000-ft., which is the main haulage adit, the mill and railroad bins being about 3000 ft. from the shaft. Orebodies were, in due time, developed on the 1000-ft. level and below. Therefore, in 1913,the shaft was sunk to the 1150-ft. level and thereafter sinking was continued at regular intervals until the 1500-ft. level was reached. But, hoisting from the 1300-ft. level was a difficult and slow process with the antiquated air hoist, so, in 1916, it was decided to raise the shaft to the surface and install a modern, electrically operated hoist. This was completed early in 1917 and the hoist was in operation in March of that year. The Hoist Figs. 2, 3, and 4 show various features of the hoist and electrical equipment. A Nordberg engine of the double-drum, geared type, designed for a 10-ton load, including rope, at a speed of 1500 ft. per min., is used. The drums are 7 ft. (2.1 m.) in diameter, with a 54-in. (137-em.)

Jan 1, 1922

By S. H. Chauvenet

The binding of the boshes and inwalls of blast furnaces has always been an expensive piece of work. When the old stone stack was replaced by the iron shell, the brickwork was kept at a thickness of five feet or more. These five-foot walls were still too thick, and the practice now is to have as thin walls as possible and to have a free circulation of air about the brickwork of the furnace. The " basket," or lattice-work biuding, accomplishes this object, but it is expensive, m to first cost, and, if any change in the diameter of a furnace has to be made, it necessitates an alteration of the binding or of the thickness of the walls.

Jan 1, 1882

By J. H. Keeler

AN alloy of zirconium containing 18 atomic pct Cb was found to be body-centered-cubic and readily deformable at room temperature. The behavior of this alloy provided an opportunity to determine if

Jan 1, 1957

By C. Williams, D. V. Carter

During 1943 five oil fields and two gas-condensate fields were discovered in the East and East Central Texas district. The New Hope field, discovered by Tide Water-Seaboard in Franklin County, is the most important oil discovery since the Hawkins field in 1940. At the close of the year two oil sands were producing and two additional oil sands were being tested. The gas-condensate fields of Appleby in Nacog-doches County and the Stewards Mill field in Freestone County had only one producing well each. The Carthage field was extended 3 miles north and 4 miles west. Another well that was testing at the year end indicated a probable eastward extension of several miles. The Quitman field, in Wood County, was the most active from the standpoint of drilling operations. Approximately 48 wells were complcted during the year. The second and third most active fields were Hawkins field, Wood County, and Kildare field, Cass County, respectively. Wartime restrictions of material, together with manpower shortage and Federal spacing regulations, reduced the number of oil and gas-well completions from 265 in I942 to 171 in 1943. This represents a drop of 35 percent, or approximately 1/3, enough to replace the 531 producing wells abandoned in the district during the year. No changes were made in the price of crude oil in the district in 1943. The district produced 177,652,940 bbl. of condensate and oil during 1943. This represents an increase of approximately 11 per cent compared with the previous year. The East Texas field, which is the largest and most important field in the district, had an annual production of 128,568,647 bbl. of oil, which is approximately 6.5 per cent more than the previous year, and represents 72 per cent of the district's production of condensate and oil for the year. The district had an estimated basic daily allowable of approximately 509,000 bbl. of oil on Dec. 31, 1943. The entire district produced approximately 30 pcr cent of the state's production for the year 1943. The Hawkins field, Wood County, was operated 271 days during the year and with an average daily production of approximately 52,488 bbl. for the year. This field, which is the second largest in the district, produced 14,224,164 bbl, of oil during the year. Changes in annual production in certain fields in the district can be attributed to their ability to produce at higher rates, the demand, and transportation facilities in the war effort. The East Texas field showed an over-all decrease in reservoir pressure of 8.30 lb. during the year. Indications were that through the first quarter of 1944 the return of salt water to the reservoir was having a beneficial effect. It is hoped that, as more and more water is returned to the reser-

Jan 1, 1944

By D. V. Carter, C. Williams

During 1943 five oil fields and two gas-condensate fields were discovered in the East and East Central Texas district. The New Hope field, discovered by Tide Water-Seaboard in Franklin County, is the most important oil discovery since the Hawkins field in 1940. At the close of the year two oil sands were producing and two additional oil sands were being tested. The gas-condensate fields of Appleby in Nacog-doches County and the Stewards Mill field in Freestone County had only one producing well each. The Carthage field was extended 3 miles north and 4 miles west. Another well that was testing at the year end indicated a probable eastward extension of several miles. The Quitman field, in Wood County, was the most active from the standpoint of drilling operations. Approximately 48 wells were complcted during the year. The second and third most active fields were Hawkins field, Wood County, and Kildare field, Cass County, respectively. Wartime restrictions of material, together with manpower shortage and Federal spacing regulations, reduced the number of oil and gas-well completions from 265 in I942 to 171 in 1943. This represents a drop of 35 percent, or approximately 1/3, enough to replace the 531 producing wells abandoned in the district during the year. No changes were made in the price of crude oil in the district in 1943. The district produced 177,652,940 bbl. of condensate and oil during 1943. This represents an increase of approximately 11 per cent compared with the previous year. The East Texas field, which is the largest and most important field in the district, had an annual production of 128,568,647 bbl. of oil, which is approximately 6.5 per cent more than the previous year, and represents 72 per cent of the district's production of condensate and oil for the year. The district had an estimated basic daily allowable of approximately 509,000 bbl. of oil on Dec. 31, 1943. The entire district produced approximately 30 pcr cent of the state's production for the year 1943. The Hawkins field, Wood County, was operated 271 days during the year and with an average daily production of approximately 52,488 bbl. for the year. This field, which is the second largest in the district, produced 14,224,164 bbl, of oil during the year. Changes in annual production in certain fields in the district can be attributed to their ability to produce at higher rates, the demand, and transportation facilities in the war effort. The East Texas field showed an over-all decrease in reservoir pressure of 8.30 lb. during the year. Indications were that through the first quarter of 1944 the return of salt water to the reservoir was having a beneficial effect. It is hoped that, as more and more water is returned to the reser-

Jan 1, 1944

By C. D. Wiseman

THE concept of alloying to increase the strength of metals originated during the bronze age. However, at the present time there is no single theory capable of explaining all of the observed strengthening effects of alloying elements on the mechanical properties. In general, it may be said that solid solutions are stronger than the pure metal and that the strengthening effect increases with increasing alloy content. Various theories for solution hardening have been proposed, the first of which was presented by Rosenhain who suggested that the alloying elements roughened the slip planes, thereby requiring a higher stress to initiate slip. Recent work by French and Hibbard2 confirmed Norbury's3 conclusion that those alloying elements which cause a greater change in lattice parameter have larger effects on hardness. However, a given change in lattice parameter produced by different alloying elements does not cause the same change in hardness. A further refinement was suggested by Dorn, Pietrokowski, and Tietz4 who considered differences in valence between the solute and solvent with the change in lattice parameter to explain the plastic properties of aluminum alloys. Allen, Schofield, and Tate5 further investigated the valency contribution to solution strengthening by testing some copper-base solid-solution alloys having constant electron densities. Tensile tests performed on these alloys gave identical stress-strain curves even though the atomic size effect, which varied by a factor of two, was neglected. The advent of dislocation theory6-8 provided a new and powerful tool capable of explaining many phenomena of plastic deformation and indicated new approaches to solution hardening. The basic con- cept of recent theories is that solution hardening is not due to stresses associated with randomly dispersed solute atoms, but rather to a nonuniform distribution of the solute. This conclusion was reached by consideration of the effective tension present on each dislocation line and the ability of a dislocation to pass an obstacle. cottrell suggested the possibility that the internal stresses due to randomly distributed solute atoms would offer essentially no resistance to the passage of dislocations. He reasoned that an edge dislocation may be considered as a rigid line discontinuity. As the dislocation moved through a crystal, the random stress fields would be equally distributed along its length. Since half of the stress fields would be acting to move the dislocation forward and the other half trying to move it back, the net effect on the dislocation would be zero. Thus the randomly distributed solute atoms would not contribute appreciably to solution strengthening. Mott and Nabarro10 considered the dislocation as a flexible, rather than a rigid, discontinuity. They obtained a simple model for a dislocation moving in a lattice having precipated particles, where the dislocation would actually bend around the obstacle until it would loop back onto itself to rejoin and then continue onward. Their work indicated that the minimum radius of curvature of the dislocation line, under the action of an external stress and in the region of an internal stress, would be such that the dislocation would be unable to pass through a matrix containing small closely spaced precipates by the looping process. The dislocations would tend to remain rather straight, approaching the condition of Cottrell's rigid dislocation. Hence, the strengthening must not be due to random solute atoms; however, it might be due to the concentration of atoms, either as clusters of like atoms or as short-range ordered regions, or to the concentration of solute atoms around dislocations. To date, four mechanisms of solution strength-

Jan 1, 1959

By M. G. Benz

The superconducting performmce of diffusion-processed Nb3Sn is influenced by its micro structure. High isotropic transverse current density may be achieved in this material by a process which forms a precipitate of ZrO, within the Nb3Sn. FOR an ideal type-I1 superconductor, little or no transport current can be carried in the mixed state; i.e., little or no transport current can be carried above the lower critical field H,,, where the field penetrates abruptly in the form of current vortices or fluxoids, even though full transition to the normal state does not occur until the upper critical field H,,.' Fortunately, nonideal type-I1 superconductors can be readily obtained and these carry large transport currents up to the upper critical field H. Both theoretical and experimental investigations have attributed this current-carrying capability for nonideal type-I1 superconductors to pinning of the fluxoid lattice by heterogeneities in the microstructure of the superconducting material. These heterogeneities may take the form of dislocations or dislocation clusters,2"5 grain boundaries: structural imperfections introduced by phase transformations; radiation damage,8"10 or precipitates.11"15 Nb3Sn formed by diffusion processing is a type-I1 superconductor. Heterogeneities are needed for high superconducting critical currents above H,,. This paper will cover: a) what the microstructure of diffusion-processed NbSn looks like; b) what changes in the microstructure take place when the system is doped with precipitates, and c) how these changes in microstructure influence the superconducting critical currents. EXPERIMENTAL Preparation of Samples. Diffusion processing was used to form the Nb3Sn. The procedure used was as follows: a) coat the surface of a niobium tape with tin; b) heat-treat this tape at a temperature above 930°C to form a layer of Nb3Sn at the Sn-Nb interface. Such a layer of NbsSn is shown in Fig. 1 The thickness of the NbsSn layer formed was controlled by the time and temperature of the heat treatment. The same general procedure was used for preparation of both undoped samples and samples doped with a precipitate. An additional step was included in the preparation of the doped samples which consisted of internal oxidation of zirconium to form ZrOn. The details of the doping process will be reported in a later paper. Sample Testing. The Nb3Sn tape samples were soldered to a copper or brass shunt. Current and voltage leads were then attached to the sample in the usual four-probe resistance measurement configuration. The sample was cooled to 42°K. In some cases it was cooled in the presence of a high magnetic field and in other cases with the field turned off. The results were the same for both cases. The samples were oriented in a configuration with field transverse to current but could be rotated such that the angle between the field vector and the wide side of the tape sample could be changed. Measurements up to 100 kG were done in a superconducting solenoid and measurements above 100 kG in a water-cooled copper magnet at the MIT National Magnet Laboratory. Once the test field was reached, the current in the sample was increased until voltage was detected across the sample. The critical current was taken as the current at which voltage was first detected in excess of background noise. In most cases this was 1 to 2 x 10~6 v for a— in.-wide sample carrying several hundred amperes with a in. separation between voltage leads and with a 10 "-ohm shunt resistance. RESULTS AND DISCUSSION Microstructure. Examination of the microstructure of the undoped Nb3Sn shows rather large-diameter (1 to 2 columnar grains growing outward from the niobium surface toward the tin surface. As the layer is made thicker by longer diffusion times, these grains grow longer. Few new grains are started. Transmission electron microscopy shows little or no second-phase material within the bulk of the Nb3Sn layer. The microstructure of a diffusion-processed NbsSn layer changes quite drastically when the system is doped so as to form a precipitate within the NbsSn layer. Instead of large-diameter columnar grains of NbaSn forming, smaller-diameter (0.5 to 1 ) equiaxed grains of Nb3Sn decorated with the precipitate form. Fig. 2 shows a transmission electron micrograph of a Nb3Sn layer doped with zirconium oxide. This layer has been etched so that one may look between the grains

Jan 1, 1969

By George A. Koenig

This new departure in assaying is the outcome of a long-felt desire to shorten the time required in muffle-assaying, as well as to do both crucible- and scarifi cation-work in one furnace. The first object in view was the gold-assay, which must always be a combination of the crucible- and muffle-work. The large lead buttons consume much time in their reduction by scorifying and cupelling. The Hoskins gasoline furnaces have been a great convenience, for years past, in that class of practice, where only one assay was required at a time. But even with them I found myself hampered, since the crucible-furnace only takes one crucible at a time, and my practice implies always duplicate assays. Another difficulty was to get the muffle up to the necessary heat and to maintain it at that heat. Whecever I had pumped myself into perspiration and out of breath, the question presented itself, " Is the muffle necessary to do this work properly ?" Hartmann and Plattner and all their blow-piping disciples have shown that very good results are obtainable by playing a direct flame upon the work-lead. Could this be done on the regular muffle-assay scale ? I placed a cupel upon a fire-brick, surrounded it with charcoal, and then played upon it with a Bunsen gas blow-pipe. The result was encouraging. With some care a 2.75-inch scorifier charged with 0.1 A. T. of a 100-ounce ore could be melted down and scorified without any apparent loss. I thought then of constructing a furnace with four blow-pipes in a row; but the combination of gas and charcoal seemed unpractical. Instead, I placed an F crucible, bottom up, in a Hoskins crucible-furnace. Upon this support I placed a charged scorifier. The rapidity with which a very refractory charge melted and scorified was simply amazing to me. Then a cupel was put in the place of the scorifier, the lid was moved sideways, and a blow-pipe was

Jan 1, 1899

By L. G. Graper, E. L. Ramsey

THE present program of increased production of armament and lend-lease material for mechanized war has created a problem for the shops that must do the machining. They have naturally turned to the steel producers to provide them with a steel that can be accurately machined with the greatest possible speed. The adding of sulphur to steel as an aid to machinability has long been practiced; however, it may cause red shortness in rolling and may result in billets with seams and cracks, which must be removed before rolling can be continued. This conditioning of billets slows down production and' adds to the cost of making steel. Experience with various grades of sulphur steel made to different specifications has shown that Bessemer sulphur steels roll better than similar grades made in the open hearth, and also that low-carbon steels that are open or semikilled .as tapped roll better than completely deoxidized or killed steels. This has led to the belief that oxygen plays an important part in the rolling qualities of sulphur-bearing steels. It is generally held that the red shortness of sulphur steels is due to the low melting point of the sulphide compounds that separate out at the grain boundaries when the steel solidifies. At the rolling temperature of steel these sulphide compounds melt and cause cracking. ADDING SULPHUR AS A SULPHITE These difficulties can be avoided if sulphur is introduced into the steel by means of an anhydrous sulphite, such as sodium sulphite or sodium bisulphite, which-upon decomposition-forms sulphur dioxide. It is assumed that, in this case, the oxygen of the sulphur dioxide forms part of the sulphide inclusions in the steel, and raises their solidification temperature enough so that the formation in the steel of a low-melting eutectic is prevented. The result is the prevention of hot shortness and a more uniform distribution of inclusions. Fig. I shows photomicrographs of steels made with sulphur, while Fig. 2 illustrates the structure of steels made with sodium . bisulphite. These samples were cut from the steels as cast-that is, before rollingand were polished and lightly etched to bring out the grain boundaries. Fig. I shows that sulphide -inclusions segregate more or less at the grain boundaries, and it can be seen how the continuity of these low-melting inclusions would cause red shortness. Fig. z shows that the sulphide inclusions are more or less uniformly distributed throughout the matrix. This arrangement of inclusions has no apparent effect on the rolling qualities of a steel. This statement has been substantiated by the observation of the rolling of over 6000 tons of steel made with a sulphite addition. RESULTS As stated before, the sulphur dioxide-is added to steel by means of the decomposi-

Jan 1, 1942

By Robert A. Laurence

Ore deposits in the Southern Appalachians are ( 1) sedimentary or syngenetic, ( 2) epigenetic, and ( 3) residual. In general, deposits characteristic of high temperature and pressure are found in the Blue Ridge and Piedmont provinces and those of low and intermediate temperature and pressure, including the sedimentary ores, are found in the Valley and Ridge and Appalachian Plateaus provinces. Residual deposits are present throughout the area. Recognition of several periods of intrusion and metamorphism in the Appalachians has changed former concepts which held that most mineralization was of late Paleozoic age in a zonal pattern including all four provinces. Many deposits probably are of early or midPaleozoic age. Similarly, recent studies in geomorphology indicate that the formation of residual deposits is a continuous process and not related to specific cycles of peneplanation.

Jan 1, 1968

By Gerald Edmunds, R. K. Waring, E. A. Anderson

Brass is liable to failure under the combined influence of stress, certain corrosion media, and time, a phenomenon commonly termed season cracking or stress-corrosion cracking. The consequences of this are serious in applications of brass generally, including the important field of cartridge cases. Cartridge cases (70 Cu: 30 Zn) that fail from this cause may allow the escape of gas from the gun breech, a hazard to the shooter, and may not eject, thus temporarily putting the gun out of action. In loaded cartridge cases, the stress present is partly residual from the, drawing and necking operations and partly applied by the insertion of the projectile. Ammonia, present as a decomposition product of smokeless powder, air and moisture constitute corrosive media. The prevalence of season cracking has been reduced considerably, but not eliminated, during the past quarter of a century by low-temperature annealing to relieve stresses residual from fabrication, a method suggested by Diegel 38 yr. ago(I).2

Jan 1, 1945

By Hans Lundberg

Jan 1, 1927

By William G. Pariseau

The extraction ratio approach to pillar design in flat seams is based on a mathematically exact analysis that is a reasonable physical approximation to room-and-pillar layouts in many instances. The essentials of the approach are reviewed and then mathematically approximate formulas for pillar design in inclined seams of arbitrary dip are proposed. Detailed numerical analysis of stress about a typical 5 entry, 4 pillar panel at dips of 0, 15, 30, 45, 60, 75 and 90 degrees at low and high extraction ratios show that the proposed inclined seam extraction ratio formulas for pillar normal and shear stresses, although conservative, have an accuracy quite adequate for engineering purposes. Appropriate pillar safety factors for compressive and shear failure and a safety criterion for overturning are specified.

Jan 1, 1982

By M. D. Hassialis, C. G. Myer

THE nature of a collector-coated mineral surface has been the subject of some experimentation and much speculation. Various aspects of the problem have been isolated and studied; it is probable, however, that there exist aspects as yet unrecognized, which are needed for a complete description of the system. The recognized elements of the problem are: 1—The nature of the chemical units comprising the film and the nature of the forces holding these chemical units to the mineral surface; 2—The orientation of the chemical units at the surface; and 3—The disposition of the collector units at the mineral surface. This report touches upon all three aspects of the broad problem; it deals, however, with a new and heretofore unrecognized element—the mobility of the collector units in the two dimensions of the solid-liquid interface. Regardless of the viewpoint adopted as to whether the chemical units comprising the collector film are collector ions or molecules, held either by chemical or physical forces, the writers on flotation theory are in apparent agreement as to the orientation of the chemical units at the mineral surface. Wark and Cox' showed that the contact angle at a stable collector-coated surface in a constant chemical environment is independent of the nature of the mineral and of any resurfacing agent; it depends solely upon the collector used. They showed further that the value of the contact angle increases with the number of carbon atoms in a homologous series of compounds. Taggart, Taylor, and Knoll2 postulated that the collector ion is oriented with the chemically reactive, polar end toward the mineral surface and the non-polar, hydrocarbon-like end toward the liquid phase. In support thereof they cited the abstraction of p-p1 dihydroxydiphenylthiourea and of glycol xanthate8 by galena without a concomitant increase in the contact angle above that of clean galena. It was argued that in these cases the water-repellent layer which normally would be presented to the liquid phase owing to the orientation of the collector ions is overlain by a layer of water-avid groups, the hydroxyl groups. Implicit is the analogous orientation exhibited by a monomolecular layer of an insoluble substance at an air-water interface. It should be pointed out that these facts also are consistent with the concept that the collector units be flat on the surface of the mineral and that the response of the surface to an air bubble is determined by the ratio of the area covered by water-avid groups to the area covered by water-repellent groups; the areas being weighted according to the relative watef-avidity or water-repellency of the groups involved. The disposition of the chemical units of the collector film at the mineral surface has not received the attention it merits. Taggart4 concluded from the observed stoichiometry of the ions entering and leaving a surface that the stoichiometry is obeyed in detail at the surface of the mineral. Thus, in the case of xanthate-coated galena, pairs of xanthate ions are attached to surface lead ions. In the case of chemisorption, Gaudin and Preller postulated an agreement between the atoms or ions of the substratum (the mineral surface) with those of the superstratum (collector film); in the case of the physical adsorption their position is not clear. In one place they state "the first type (physical adsorption) does not require any agreement between the atoms or ions of the substratum with that of the superstratum" and in another place that "It seems, in fact, as though some slight influence of the substratum is formed even in physical adsorption." The present work shows that in some cases of chemisorption the chemical units of the collector film are in constant surface-bound motion and may not be assigned to any site of the surface, hence there is no permanent association between the chemical units of the film and the atoms or ions of the solid. The physical property of the collector film that is of paramount importance is its surface energy. Although this property is not susceptible to direct experimental determination, the related contact angle is. Much of the knowledge of the properties of a collector film derives (by deductive and inductive reasoning) from the behavior of an air bubble thereat

Jan 1, 1952

By Charles H. Jacoby

Solution-mined salt cavities are being used for storage of liquid petroleum gas, natural gas, and other hydrocarbons; waste disposal or storage; storage of radioactive wastes; and as a surge vessel for air compressed by an electric utility during off-peak hours. Examples of each use are given. Other contemplated uses of salt cavities are noted.

Jan 1, 1973

By J. E. Campbell, G. D. Calkins, N. M. Ewbank, M. Pobereskin, A. Wesner

GRINDING for size reduction affects the economics of many processes and products. It is essential as the first step in many industrial processes and is also a finishing step for materials with properties depending on particle size, such as talc, cement, and silica sand. Intermediate and fine grinding are vital operations in the U. S. cement industry, which is producing more than 250 million bbl of cement per year.' Wear of the grinding media is a large part of the grinding operation cost. Problems encountered in grinding cement are so complex that evaluation of efficiency and economy of grinding media is difficult.2 It has been especially difficult to evaluate the relative effectiveness of different types of balls because there are no good testing techniques. Many other industrial operations can be evaluated on a laboratory scale with reasonable accuracy. This does not hold true for evaluation of grinding balls. The consistent results obtained in a laboratory test under a given set of conditions are not always borne out in field application. Rough evaluations of the effectiveness of various compositions and types of grinding balls have been made in the field by using a full charge of one type in a mill and comparing the production record with another run using another type of ball. This method is time-consuming and not very precise, as the second run may not have been carried out under identical conditions. Laboratory-scale tests, on the other hand, have yielded inconclusive results, and many investigators have turned their attention to the development of a field testing technique. Field testing small sample lots of grinding balls has been impractical because it is difficult to identify and recover the test specimens from the grinding mill, and individual groups of balls that have undergone different heat treatments can not be separated.".4 To overcome these difficulties, previous investigators have identified the balls by distinctive marks, notches, and drilled holes, but this procedure has three serious drawbacks: 1) Grinding characteristics and quality of the steel balls may be affected. 2) Physical markings may be worn away in the grinding process, especially during a prolonged run. 3) Recovery from the bulk of the charge will be extremely difficult because the markings are hard to see and may be masked by a coating of the product. To circumvent these difficulties, a radioactive-tracer technique was proposed for recovery and separation of steel grinding balls and subsequent evaluation of the various compositions of the balls. The proposed technique involved five basic operations: 1) Thermal-neutron irradiation activation5 of each group of test grinding balls to a different level of specific radioactivity. 2) Addition of groups of radioactive steel-ball specimens into a ball tube mill. 3) Recovery of radioactive steel-ball specimens from the bulk of the mill charge. 4) Separation of the various groups by their specific radioactivity. 5) Evaluation of actual grinding ball wear. Before any physical tests were performed, required neutron irradiation intensity and time were calculated. Probable composition of the steels to be used was ascertained. An examination was made of the radioactive nuclides8 to be formed which would contribute measurably to the radiation level immediately after irradiation and during the test operation. The radioisotopes formed, their types of radiation, and their half lives are listed in Table I. Of these radioisotopes only iron-59 and chromium-51 were significant for the actual wear test. The intensity of radiation that could be detected by a Geiger counter when the test was completed was the basis for the minimum activation level established. The intensity of radiaton that could be safely handled at the beginning of the test was the basis for the maximum activation level, although this was not considered a major problem. Ten groups of grinding balls of various composition and/or surface or heat treatment were to be tested. One group was designated for the minimum irradiation time. The remaining groups were designated for irradiation periods that increased by increments of 33 pct from that of each preceding group. This difference was considered enough for separation and identification of the groups by comparison of specific activity. Potential Hazards: Possible radiation hazards that might be encountered during this experiment were evaluated for the three important phases: 1) the radiation hazard of placing balls and removing them from the mill, 2) contamination of the product cement by radioactive material worn from the balls, and 3) contamination of the steel by the radioactive balls left in the mill. The radiation intensity expected from the whole group of radioactive balls was calculated to be 250 milliroentgen per hr at 1 ft. This meant the balls would require special shielded packaging and warning labels on the shipping containers. In a radiation field of 250 mr per hr a man can work for 1 hr without exceeding maximum permissible weekly exposure. Since the balls could be dumped into the mill in a matter of seconds, relatively little radiation exposure was anticipated at this stage of the operation. If the weight loss in the balls was 7.7 pct per month and the cement feed through the mill was

Jan 1, 1958

By F. G. Tahmoush, N. J. Grant, E. P. Abrahamson

The effect of grain size on the brittle -ductile transition temperature of pure iron and three dilute Fe-W alloys has been investigated by slow bend tests. The brittle-ductile transition temperature for pure iron increased with increasing grain sizes from 8000 to 500 grains per sq mm where the transition temperature then decreased with further increase in grain size. The dilute additions of tungsten lowered the transition temperature for fine grain sizes, suppressed a reversal of the curve in the coarse grained portion, and raised the transition temperature for this region. The frequency of twin occurrence increased with increasing grain size and decreasing temperature. The object of the present investigation was to re-examine the effect of grain size on the brittle -ductile transition of pure iron and several dilute Fe-W alloys. Current literature normally presents a simple relationship between grain size and the brittle-ductile transition temperature, namely, that the transition temperature increases with increasing grain size. Heslop and etch' have studied the transition temperature of mild steel by V-notch Charpy impact tests for the grain size range between 200 and 6000 grains per sq mm. The result was a linear plot of In 1-1/2 vs brittle-ductile transition temperature, where 1 is the grain diameter. Recent experiments by sipos2 revealed the possibility of a reversal in the slope of the grain size vs transition temperature plot for pure iron; however, his investigation was limited in scope, and the data obtained were insufficient to permit a definitive curve. The present investigation was undertaken in an effort to confirm or extend the grain size effect observed in iron by Sipos. PROCEDURE All alloys were vacuum induction melted, using 99.95 pct Fe containing 0.03 pct 0 and 0.004 pct C. Four ingots were made, ranging from pure iron to iron with 0.035 pct W. The chemical composition of each alloy, after processing, is given in Table I. The four alloys were prepared as 45 lb heats and cast into 4 in. diam by 16 in. molds. They were then extruded into 3/4 in. rods at 1800oF. Specimens for chemical analysis, taken from various positions along the rods, revealed no variation in tungsten content along the length. The extruded rods were reduced to 0.156 in. diam stock by a series of cold swaging operations involving intermediate vacuum annealing treatments. This procedure yielded a final cold reduction in area ranging from 10 to 90 pct. The swaged rods were chemically cleaned, cold pressed to a cross section of 0.10 by 0.18 by 1.0 in. long (2.54 by 4.73 by 25 mm). The specimens were wrapped in iron foil and vacuum sealed (10-4 mm Hg) in quartz. Various heat treatments at temperatures from 700" to 1300oC were utilized to produce grain sizes from 8000 to 1 grain per sq mm. Grain sizes were determined by measuring the average area of grains in a polished section. In specimens with grain size greater than 20 grains per sq mm, the total number of grains in the cross section was counted and then divided by the area to yield grains per sq mm. Grain size was measured both for longitudinal and transverse cross sections. The average of the two measurements was plotted vs transition temperature. An Instron Table Model testing machine was used to determine the transition temperature of specimens tested in three point horizontal bending. The specimen was supported by two 1/4 in. dowels one in. apart. Bending was accomplished with a push rod, the end of which had an 1/8 in. radius. The head speed was 50 in. per min. Temperatures were established through the use

Jan 1, 1963

By O. Hyvärinen

The treatment of anode slimes at Outokumpu Pori Copper Refinery comprises the following process stages: copper leaching by air oxidation, nickel removal by digesting slimes in concentrated sulphuric acid at 200 °C, and dissolving of the formed nickel sulphate into water, roasting of the slimes in controlled gas atmosphere at 600 °C for selenium removal, smelting of slimes in a Doré furnace, electrolytic refining of silver, sulphuric acid and aqua regia leaching of slimes from the silver cells followed by the reduction of gold and platinum metals. The paper discusses operational experiences and recent developments of the process.

Jan 1, 1984