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Jan 1, 1969

By H. C. George

The Wisconsin Zinc District, or the Upper Mississippi Lead and Zinc District as it is often called, lies in the southwestern corner of Wisconsin, in Grant, Iowa and Lafayette Counties, and it includes adjoining parts of Illinois and Iowa. The district is about 70 miles long, north and south, and about 40 miles wide, east and west. It lies wholly within what is geologically known as the non-glaciated area of the Upper Mississippi Valley. HISTORY OF THE DISTRICT The district was first opened up as a lead producer in 1822. From this time until 1860, about 205,000 tons of cog lead (galena) and washed lead (galena) was produced from shallow crevices and openings. From 1860 to 1900, about 74,500 tons was produced, and since that time, from 5000 to 7000 tons has been produced annually. Since 1900, most of the lead concentrate produced has been as a byproduct of the zinc mines. The first zinc ores were mined about 1862. These were the carbonate ores, locally known as "drybone." Very little zinc blende was mined in the district, previous to 1875. The zinc blende ores mined from 1875 to 1900 were mostly of the high-grade, hand-cobbed, sheet-ore class, which usually contained from 45 to 60 per cent. metallic zinc Such mines as the "Sallie Waters," "Quinlin," 'Lead Mine," "Benton Blende," and "Ida Blende," located near Benton, Wis., were mines which produced ores of this type, during this period. The mines located at Highland, the "Coker Mine" located at Livingston, Wis., and the "Opencut Mine" located at Shullsburg, Wis., were mines that were heavy zinc carbonate producers, previous to 1900. The production of zinc ores in the district from 1862 to 1890 was about 283,500 tons, mostly zinc carbonate, with a probable average metallic zinc content of 30 per cent. From 1890 to 1903, the production

Jan 1, 1918

By Eugene A. Stephenson

NUMBER of noteworthy events in the petroleum industry may be reported for 1941, of which the most spectacular was doubtless the rise in the daily rate of crude-oil production to a peak of approximately 4,300,000 barrels. This enormous daily rate did not ensue from the furor of flush pools but represented for the most part merely a slight additional daily delivery from many wells that had previously been operated on a more restricted basis, in line with good conservation practice and also from the adroit increase in the number of days per week by the Texas Railroad Commission. Another important fact was the increase in price throughout the Mid-Continent area from the static level of $1.02 for 36°, A.P.I., crude, to $1.17 per barrel. Efforts to elevate the price above this point have met with severe opposition from the O.P.A.. as has also a similar effort by the PennsyIvania Crude Oil Producers' Association, but the vastly increased costs for materials and labor may shortly give the industry the enhanced price which it has long deserved.

Jan 1, 1942

By P. B. Bucky

IN this day of steady progress in the mining industry, especially along mechanical lines, the question of whether to discard present equipment for that of a new type often engages the minds of many officials of mining companies. The rapid strides made from year to year sometimes cause this question to be brought up within a year after new equipment has been purchased and installed. It is a moot question whether a machine that has been purchased last year should be replaced by a new one put on the market this year. As I see it, the reasons for the replacement of present equipment may be summed up as follows: (1) because of increased safety; (2) because of legal regulations; (3) because of increased profits. I think all of us, as engineers, will endeavor to put in as safe equipment as it is possible to devise. The tendency of mining companies in that direction is very gratifying.

Jan 1, 1930

By Raymond C. Boettner

The present work had for its purpose: 1) the identification of crack nucleation sites in AISI 4340, quenched to martensite and tempered over a range of 'temperatures; and 2) the comparison of fatigue processes in AISI 4340 with processes observed previously in pure metals From constant def1ection-bending fatigue tests, martensite boundaries were identified as the favored crack nucleation sites in quenched and tempered AISI 4340. It, also, was concluded that the fatigue processes operating- in this lous-alloy steel were similar to Processes observed in pure tnetals. ALTHOUGH much engineering data has been accumulated on the fatigue properties of quenched and tempered martensitic steels,' fatigue as a process is not as well understood in martensite as it is in pure metals.' Important features of the fatigue process, such as the identity of the nucleation sites, have not been determined in the commercially important high-strength low-alloy structural steels. The present work had for its purpose: 1) the identification of crack nucleation sites in a low-alloy steel, i.e., AISI 4340, which had been quenched to martensite and tempered over a range of temperatures; and 2) the comparison of fatigue processes in the AISI 4340 with processes observed previously in pure metals. This comparison of the fatigue processes in the different tempers was restricted to the high-strain low-cycle part of the S-N curve. Under these test conditions, previous work on a number of metals has shown that a large number of cracks are nucleated in less than 30 pct of the fatigue life.3 Furthermore, crack nucleation sites are not restricted to inclusions but are also associated with intrinsic structural characteristics of the metal. MATERIAL A 20-lb ingot of vacuum-melted AISI 4340 (for composition see Table I) was hot-rolled to 1-in.-diam rod and then cold-rolled to a 1-in.-wide strip, 0.08 in. thick. Fatigue specimens, see insert of Fig. 1, were machined from the strip with the long dimension parallel to the rolling direction. m this orientation, the stringers of 1 to 2 p inclusions present in the sheet lay parallel to the stress axis in the specimens. The specimens were austenitited at 2050°F in order to obtain a large prior austenite grain size, i.e., 2 mm, which facilitated the subsequent identification of the prior austenite boundaries. A helium atmosphere was used to minimize decarburization. After austenitiza-tion at 2050°F, the specimens were transferred to a 1450°F furnace so that specimen distortion was held to a minimum in the subsequent oil quench. Previous work4 indicated that refrigeration in liquid nitrogen prior to tempering reduced the percentage of retained austenite in the quenched specimens to less than 5 pct. Tempering was carried out in air over the temperature interval of 200°to 800°F to produce a range of mechanical properties, Table I. The preparation of the fatigue specimen was completed by grinding about 0.005 in. from each surface and electropolishing in a chrome trioxide-acetic acid solution for 30 min. Examination of etched cross sections of specimens prepared in this fashion showed the foregoing specimen preparation to be adequate for the removal of the decarburized layer present after the heat treatment. Transmission electron microscopy showed that the as-quenched microstructure of this alloy consisted of a mixture of martensite plates containing either a high density of dislocations or microtwins. Previous work5'6 indicated that in the course of oil quenching autotem-pering resulted in the formation of E carbide on the martensite and microtwin boundaries. Tempering for 2 hr at temperatures up to about 400°F resulted in further precipitation of the E carbide. Finally, at about 400°F, cementite began to replace the E carbide on the martensite and microtwin boundaries in addition to forming a Widmanstatten structure within the plate matrix. EXPERIMENTAL S-N curves were obtained using electropolished specimens cycled at 1800 cpm as cantilever beams in fully reversed bending at selected constant deflections. The deflections were translated into surface strains by means of a calibration curve obtained through the use of strain gages. An argon atmosphere was used to minimize environmental effects. To investigate the development of fatigue slip bands, the specimens of the different tempers were unidirec-tionally bent to a surface strain of 0.005 to 0.007, photographed to record the location and appearance of slip bands so introduced, and then cycled to failure

Jan 1, 1968

By H. T. Kennedy

The fact that intrusion of water into oil wells can be prevented by treating the sand adjacent to the well seems to have been only recently recognized. Swan1 mentions the process of solidifying naphthalene in strata. R. Van A. Mills2 recommends the use of materials such as sodium silicate and sodium carbonate, which react with oil-field water to form solid plugging agents. When a well is drilled in a new field the oil sands are found essentially devoid of water (Fig. 1). Unless a completely impermeable break exists over wide areas in the field, no water is found above the lower limit of the oil zone and no oil is found below the upper limit of the water zone. After considerable oil has been taken from the well, however, it is almost universal experience that water intrusion occurs. This intrusion may be of two kinds. The water may follow a path parallel to the bedding planes of the producing formation through loose streaks in the pay sand, as shown in Fig. 2, or the water level of the field may rise and enter the well by coning (Fig. 3). Water entering from the side is called "edge water," and that coming in from the bottom is called "bottom water.'' Effectiveness of any method for shutting off water depends not only on the effective treatment of the sand adjacent to the well but on

Jan 1, 1936

By H. T. Kennedy

The fact that intrusion of water into oil wells can be prevented by treating the sand adjacent to the well seems to have been only recently recognized. Swan1 mentions the process of solidifying naphthalene in strata. R. Van A. Mills2 recommends the use of materials such as sodium silicate and sodium carbonate, which react with oil-field water to form solid plugging agents. When a well is drilled in a new field the oil sands are found essentially devoid of water (Fig. 1). Unless a completely impermeable break exists over wide areas in the field, no water is found above the lower limit of the oil zone and no oil is found below the upper limit of the water zone. After considerable oil has been taken from the well, however, it is almost universal experience that water intrusion occurs. This intrusion may be of two kinds. The water may follow a path parallel to the bedding planes of the producing formation through loose streaks in the pay sand, as shown in Fig. 2, or the water level of the field may rise and enter the well by coning (Fig. 3). Water entering from the side is called "edge water," and that coming in from the bottom is called "bottom water.'' Effectiveness of any method for shutting off water depends not only on the effective treatment of the sand adjacent to the well but on

Jan 1, 1936

NEW YORK MEETING PAGE Winchell, H. V.-Geology of Pachuca and El Oro, Mexico. Discussed by Frederick MacCoy, Robert Hawxhurst, Jr 2 WILKES-BARRE MEETING Kynor, Herbert D.-Mechanical Mining of Anthracite. Discussed by C. Evans, Jr., S. J. Jennings, W. J. Richards, Geo. S. Rice, and the author 3 Stein, C. H.-Ashley Planes for Handling Freight Traffic. Discussed by Graham Bright, Douglas Bunting, S. J. Jennings, R. V. Norris, C. H. Strange, Edwin Ludlow, W. J. Richards, and the author 3 Markle, Donald.-Anthracoal: A New Domestic and Metallurgical Fuel. Discussed by William Griffith, Edwin Ludlow, E. M. Chance, Charles Dorrance, E. W. Parker, G. H. Ashley, C. A. Burdick, Geo. S. Rice, and the author :.. 7 Griffen, John.-Slush Problem in Anthracite Preparation. Discussed by Henry Flood, Jr 11 Eavenson, H. N.-Lynch Plant of United States Coal and Coke Co. Discussed by E. V. d'Invilliers, C. Evans, Jr., Graham Bright, Geo. S. Rice, Geo. Otis Smith, A. M. Rodgers, C. T. Starr, C. A. Burdick, and the author 15 Bunting, Douglas.-Mine Fires Extinguished by Sealing. Discussed by Geo. S. Rice, J. B. Warriner, H. H. Otto, Edwin Ludlow, E. M. Chance, F. B. Nold, H. M. Chance, W. L. Jacobus, J. A. S. Ritson, R. D. Hall, Geo. S. Rice, and the author 18 Bright, Graham.-Determination of Electrical Equipment for a Mine Hoist. Discussed by F. L. Stone, Geo. S. Rice, L. F. Mitten, and the author 34

Jan 12, 1921

By Gordon E. Agar

Several correlations have been proposed to relate energy consumption and size reduction in comminution, and although these are arrived at from different starting points, it is postulated that they are all statements of the same basic concept. To test this postulate, the dry ball mill grindability of langbeinite was determined, and the results were analyzed according to the various methods. An examination ' of the energy-particle size relationships proposed in the recent past revealed that they had much in common. In fact, the conclusion was tentatively drawn that these expressions were essentially the same, even though they were arrived at from quite different basic premises. The equations attributed to Charles2 and Holmes3 were shown to re- duce to the same single equation, W - A K-3, and the simulated continuous test used by Maxson et al.4 was shown to give the best experimental value of the required empirical parameter, ß. Furthermore, the size distribution parameter a in the Schuhmann equation, y - (x/K)2, was shown to be equal to ß in many cases. The kinetic approach used by Arbiter and Bhrany5 should give the same results as the Maxson test procedure; however, the batch operation used by Arbiter and Bhrany could not produce data that would be as precise as the simulated continuous technique. To test the validity of these conclusions, the simulated continuous method was used to obtain data on the dry grinding of langbeinite. The results are discussed in terms of the various equations and approaches. APPARATUS AND MATERIAL A ball mill with internal dimensions of 17.5 cm (6 7/8 in.) in length by 19.4 cm (7 5/8 in.) in diam was loaded to 50% of its volume with balls 3.2 cm in

Jan 1, 1969

By I. Plaskin

Interaction of sulfide minerals and native metals I with reagents in flotation is largely determined by particle-surface changes resulting from action of the medium and dissolved gases. A number of early studies were devoted to the selective action of various gases on minerals.' Mc-Lachlan' paid attention to oxygen as the most active gas affecting flotation properties of sulfide minerals. Opposing views were expressed concerning the influence of sulfide oxidation on xanthate flotation: Taggart3 recognized the positive influence of oxygen, and I. W. Wark4 rejected it. Shvedovh ffered the hypothesis of partial oxidation. As to the influence of such gases as hydrogen" and carbon dioxide on mineral floatability, opinions also differed. Effect of Oxygen on Sulfide Mineral Flotation: Research on the influence of oxygen and other gases on the floatability of sulfide minerals and native metals has been carried out at the Institute of Mining of the USSR Academy of Sciences in

Jan 1, 1960

By E. Maltby Shipp

WALLACE MCKEEHAN, Douglas, Ariz. (communication to the Secretary*).-In going over this report, which I have done very carefully, I find that the summary as composed deals with the various problems almost entirely from the employer's standpoint and that practically no consideration is given to the employee's point of view. An experience of 3 ½ years as safety inspector, and almost 30 years as workman-and official, has convinced me that any plan for the betterment of working conditions which will achieve any degree of success must give the workmen their share of responsibility and allow them full participation. The company may finance and direct the movement, but its ultimate success depends upon the support given by the workmen. The cooperation of the men doing the actual work is so essential that all writers insist that this must he secured, but they do not agree as to how this can best be done.

Jan 3, 1917

By F. A. Veer, W. G. Burgers, B. H. Kolster

Starting-- from Cu-Si diffusion couples a study of diffusion in the intermetallic compound Cu3Si of the Cu-Si system has been made. Mmker experiments showed copper to be the diffusing element. From the rate of growth of the Cu3Si phase diffusion coefficients were derived. The activation energy for diffusion is 18.6 kcal per mole. The couples show some interesting microscopic features, for which a tentative explanation is given. THE synthesis of dimethyldichlorosilane, (CH3)2SiC12, an important compound in the manufacture of methyl-silicones, takes place at the surface of a thin Cu3Si layer deposited on a mass of silicon particles."' By passing CH3C1 vapor at about 350°C, silicon atoms are consumed from Cu3Si in forming the volatile silane molecules, thus leaving copper atoms at the surface. It is well-known that copper acts as a poison for the above-mentioned reaction by catalyzing the dissociation of methylchloride.' However, no poisonous effect is observed, at least not before most of the silicon from the particles is converted into silane.3 This would be understandable, if either the copper atoms diffuse through the Cu3Si deposit to the underlying silicon or silicon atoms diffuse in the reverse direction to the copper, both processes resulting in the formation of new Cu3Si and so ensuring the proceeding of the reaction. In this paper experiments are described, demonstrating copper to be the diffusing element. Also a very low activation energy for the diffusion is observed. EXPERIMENTAL The silicon used contained 1 ppm Mg and 1 ppm Cu; the copper was spectroscopically pure (Fe: 2 ppm; Ag, Mg, Si: 1 ppm). The copper and silicon samples were prepared in the form of blocks of approximately 10 by 10 by 5 mm with two parallel sides by spark-machining. The blocks were ground on emery paper (grit 600), etched (copper with nitric acid, silicon with a 4:l nitric acid:hydrofluoric acid mixture), and cleaned with alcohol. As the brittleness of the silicon did not allow a welding procedure to prepare the diffusion couples, the copper and silicon blocks were pressed together in a steel clamp. The pressure exerted by the clamp brought about contact between the parts of the couple and so ensured proceeding of the diffusion. The couples were heated in a vacuum furnace (about 10"5 Torr). The temperature was stabilized within 1 pct. After a heat treatment a section parallel to the direction of diffusion was examined in the microscope and in the X-ray scanning microanalyzer. To determine whether copper or silicon is the diffusing element marker experiments were carried out using tungsten wires with a 20-p diam. EXPERIMENTAL RESULTS Figs. 1, 2, 3, and 4 give micrographs of diffusion zones of Cu/Si couples. Analysis by the electron mi-croprobe of the Cu/Si samples after a definite heat treatment revealed the existence of only one intermetallic phase as can be seen from the line scan shown in Fig. 5. From the X-ray diffraction pattern it could be deduced that this phase was CU 3 Si.4 Even when diffusion zones of considerable width (up to 600 p) were obtained, no other phases occurring in the Cu-Si system could be detected, neither by the electron microprobe nor by X-ray diffraction analysis. The optical anisotropy of the Cu3Si phase made it possible to observe the columnar shape of the crystal-

Jan 1, 1969

By R. J. Reynik, F. R. Meeks

IN the classical paper1 of Mehl and Rhines entitled "The Rates of Diffusion in the Alpha Solid Solutions of Copper", the authors state: "It has been mathematically demonstrated that the treatment of the data as though the diffusion were taking place between two flat plates instead of radially in a cylinder has no appreciable effect upon the results. Were the bars of a much smaller diameter, a modification of the analytical treatment would have been required." Unfortunately, the errors in the reported concentrations are much too large to neglect, as shown in the results below. A planar treatment of diffusion data assumes that the reference planes separated by a nominal distance (AX) have identical areas. An adjustment must be made on the concentration data should the successive diffusion planes differ in area. The Mehl-Rhines' diffusion samples were cylindrical with copper electroplated onto copper-based alloys. Successive surface areas through which diffusion occurs are in the ratio ri/r1, where ri is the radial distance between the center of the sample and the center of the i th shell to which the host (alloy) atoms diffuse, and r1 is the radial distance between the center of the sample and the center of the innermost (i = 1) experimentally reported shell from which the alloy atoms diffuse. Hence, ri/r1 (i = 1, ..., n layers) is a dimensionless correction factor to be multiplied by the reported concentration data before planar-data analysis is attempted. In the forty-seven samples reported, the original interface between the copper alloys and the electroplated copper was located at a mean distance of 8.255 mm from the center of the samples. The successive layers, machined off the samples, were approximately 0.0762 mm thick. The distance (xi) at which concentration (ci) was reported was always a distance measured with respect to the original interface, that is, with respect to the fixed distance of 8.255 mm. Hence, the as yet undiscovered Kirkendall Effect was precompensated. The values of ri and r1 are therefore given by ri = 8.255 + xi and Y, = 8.255 + x,. The illustrative table below lists the position xi (mm), ri (mm), the value of ri/r1, the reported concentration (ci) in weight percent (only valid for radial analysis of data), and the corrected concentration [c'i = (ri/r1)ci] in weight percent (only valid for planar analysis of data). Similar tables can be constructed for the remaining forty-six samples. The corrected data can be used to re-evaluate the diffusion coefficients for the reported systems.

Jan 1, 1965

By G. Krauss, J. M. Thompson, H. Y. Kumagai

Boron-doped p-type and arsenic-doped n-type source materials were used to deposit thin silicon films on amorphous fused quartz substrates by cathodic sputtering in argon atmospheres. All as-sputtered films were found to have high electrical resistivities of about 104 ohm-cm, despite controlled variation of the substrate temperature from 50O to 400°C. The high resistivity of the n-type films persisted even after postdeposition heat treatments as high as 1000°C, while p-type films showed a sharp decrease in re-sistivity to values on the order of 1 ohm-cm or lower after heat treatments above 650°C. X-ray and electron diffraction, together with transmission electron microscopy of the p-type films, revealed that the improved electrical properties resulted from two distinct processes. A primary crystallization or recovery within the pains, which were approximately 200Å diam in the as-sputtered films, accompanied the initial sharp drop in resistivity at 650°C. Following this process, a secondary recrystallization or discontinuous grain growth was nucleated in films heated at 1000°C. The resulting significantly increased size of certain grains and the corresponding decrease in grain boundary area accompanied an additional decrease in resistivity after heat treatment at 1000°C. The properties of thin silicon films are of interest because of their possible application in device technology. Although evaporated silicon films on amorphous substrates1-3 and both sputtered and evaporated germanium films4-' have been studied in some detail, sputtered silicon films have not been widely investigated. It has been observed that evaporated silicon films deposited at substrate temperatures below approximately 600°C are amorphous.1,3,9,10 At substrate temperatures higher than this, the films are polycrys-talline, sometimes exhibiting a fiber texture with the fiber axis normal to the substrate surface.' Similar results have been obtained with germanium films, although in this case the substrate temperature for the amorphous to crystalline transformation is reported to be as low as 150OC.5 The mechanism of film deposition by cathodic sputtering differs markedly from that of thermal evaporation. It might be expected, therefore, that the properties of sputtered and evaporated silicon films would also differ. The purpose of our study was to determine the effects of deposition conditions and heat treatments on the electrical resistivity, structure, and composition of thin silicon films sputtered on fused quartz substrates. EXPERIMENTAL DETAILS Apparatus. A schematic diagram of the sputtering apparatus is shown in Fig. 1. The vacuum chamber was enclosed by an 18-in.-diam by 12-in.-high Pyrex bell jar mounted on a stainless-steel base plate. Access holes in the base plate were used to supply argon gas to the chamber, to allow for various electrical feedthroughs, and to provide mechanical motion to the shutter between the source material and substrate. The chamber was evacuated by a pumping system consisting of a 720 liter per sec oil diffusion pump backed by a 13 cu ft per min mechanical pump. Ultimate pressures of less than 1 x 10-6 torr could be achieved. The substrates were securely mounted on the stainless-steel substrate holder by quartz tabs held in place by stainless-steel screws. Temperatures of the substrate holder were measured by a thermocouple inserted within the holder. A quartz lamp was used to heat the holder and temperatures as high as 420°C could be maintained. Deposition Conditions and Procedure. The substrates used were polished fused quartz slides 116 by 1-12 by 3 in. and were outgassed at 200°C for 1 hr at a pressure less than 1 x 10-5 torr before film deposition. This was followed by a presputtering period of 2 hr during which the movable stainless-steel shutter was so positioned that deposition on the substrate was prevented. At a sputtering voltage of 5000 v dc and an argon pressure of 0.03 torr, the cathode cur-

Jan 1, 1967

By Michael F. Dunn, Francis S. Kendorski

The fall of rock from strip coal mine highwalls continues to be the largest single source of fatal accidents, so methods to improve highwall stability through improved blasting practices were investigated in the field. This paper covers the results of a project to improve, using existing and proven technology, unstable highwall conditions through better blasting practices in Appalachian strip coal mines. Better borehole blasting agent distribution and optimization of burden, spacing, and delay periods allowing satisfactory breakage with minimal backbreak were the objectives. At a selected field site, geologic conditions were closely examined with regard to joint orientation and spacing, and resulting slope stability considerations. Utilizing surface blasting concepts of trying to achieve flexural failure of the rock mass both horizontally and longitudinally by appropriate relationships between burden, spacing, and hole length, as well as delay time sequence to achieve optimal confinement and breakage, successful results were achieved. A test series of eight blasts was completed and the resultant highwall monitored by repetitive photography. Actual blockfalls could be measured and the stability for each blast design thus quantified. The study of drilling and blasting economics along with equipment performance led to an economic model of blast parameters and the identification of blast design cost benefits. The work demonstrated that small strip mining companies are able to achieve a more stable highwall excavation utilizing presently available technology, equipment, and explosive products at improved operational cost and safety.

Jan 1, 1983

By T. M. Morris, W. E. Horst

W. E. Horst—In regard to the flotation rate being described as "first orcler" for flotation of quartz particles below 65 p in size (or any size studied in this work) in this paper, it appears that the authors' conception of rate equations is not in agreement with cited references. A first order rate equation has as one of its forms the following: a In.=a/a-x=kt where a = initial concentration, a—x = concentration at time t, t = time, and k = constant. The constant, k, has the dimension of reciprocal time which is similar to the specific flotation rate, Q. described by Eq. 2 in the authors' article, as has been previously discussed by Schumann (Ref. 1 of original article). The plotted data presented in Fig. 4 of the article utilizes the specific flotation rate, Q (min.'); however, there is not adequate data given to indicate the order of the rate equation which describes the flotation behavior of the quartz system studied. Results from the experimental work indicate that the relationship between rate of flotation (grams per minute) and cell concentration (provided the percent solids in the flotation cell is less than 5.2 pct and the particle size is less than 65 p) is described by an equation of the first order (R, = k c+", n being equal to 1 in this size range) and the use of the first order rate equation does not apply. Similarly the relationship for other particle size ranges studied is expressed by equations of the second or third order depending on the magnitude of n. T. M. Morris—The authors are to be commended for the experiments which they performed. As they state in their discussion the concentration of collector ion In solution did change with change in concentration of solids in the flotation cell. Since for a given slze of particle, flotation rate increases with concentration of collector until a maximum is reached, the effect of concentration of particles in their experiments was to vary the concentration of collector ions. A collector concentration which insures maximum supporting angle for all particles eliminates the unequal effect of collector concentration on various sized particles and the effect of size of particles and concentration of particles upon flotation rate could be more clearly assessed. I believe that if the authors had increased the concentration of collector to an amount sufficient to attain a maximum supporting angle for all particles they would find that the specific flotation rate of particles coarser than 65 p would be constant with change in the concentration of solids in the flotation cell, and that a first order rate would apply to the + 65 as well as to the —65 p sizes. It might also be discovered when this change in collector concentration was made that the maximum specific rate constant would be shifted toward a coarser fraction than when starvation quantities of collector are used since this practice favors the fine particles and penalizes the coarse particles. P. L. de Bruyn and H. J. Modi (authors' reply)—The authors wish to thank Professor Morris for his kind remarks and for mentioning the influence of equilibrium collector concentration on flotation rate. With a collector concentration sufficient to insure maximum supporting angle for all particles, a first order rate equation may indeed be found to be generally applicable irrespective of size. Such a concentration would, however, lead to 100 pct recovery of the fine particles and consequently defeat the essential objective of the investigation to derive the maximum information on flotation kinetics. To establish absolutely the validity of any single rate equation for a given size range, the ideal method would be to work with a feed consisting solely of particles of that size range. Use of such a closely sized feed would also eliminate the possibility of the interfering effect of different sizes upon one another. The authors do not believe that increasing the collector concentration would shift the maximum specific flotation rate (Q) towards a coarser fraction. Experimentation showed Q to be independent of solids concentration for all particles up to 65 µ in size, whereas the maximum value of Q was obtained in the range 37 to 10 p. Professor Morris contends that the addition of starvation quantities of collector favors fine particles at the expense of coarse particles, but the reason for this is not entirely clear to the authors. The comments by Mr. W. E. Horst are concerned only with the concept of the term "first order rate equation." According to the usage of this term in chemical kinetics, time is an important variable, as is shown in the equation quoted by Mr. Horst. All the experimental results reported by the authors were obtained under steady state continuous operations when the rate of flotation is independent of time. To be consistent with the common usage of the "first order rate equation," it would be more satisfactory to state that under certain conditions the experimental results show that the relation between flotation rate and pulp density is an equation of the first order.

Jan 1, 1957

By Charles E. Lundin

Pressure-temperature-composition data were obtainedfor the Er-H system. Measurements werecar-ried out in the temperature range of 473° to 1223°K, the composition range of erbium to ErH,, and the pressure range of 10-5 to 760 Torr. Solubility relationships were established from these data throughout the system. Three solid-solution phases were delineated: metal solid solution, dihydride phase, and trihydride phase. The trihydride Phase decomposes at about 656°K and 1 atm pressure. The dihydride phase is stable to about 1023°K, but becomes more deficient in hydrogen above this temperature. The equilibrium decomposition pressure-temperature relationships in the two-phase regions, erbium solid solution plus dihydride and dihydride plus trihydride, were deter- The differential heats of reaction in these two regions are AH = - 52.6 * 0.3 and - 19.8 i 0.2 kcal per mole of Hz, respectively. The differential entropies of reaction are AS = - 35.2 * 0.3 and - 30.1 * 0.4 cal per mole HZ.deg, respectively. Relative partial molal and integral thermodynamic quuntities were calculated in the system to the dihydride phase. RARE earth metal-hydrogen systems have been the subject of general survey,1"4 and all have been found to form hydride phases. The heavy rare earths, of which erbium is a member, form dihydride and trihydride phases with different crystal structures, whereas the light rare earths form only a single-phase dihydride which expands without structure change, as hydrogen is added, to the trihydride composition. These materials are of interest primarily because of their theoretical properties, such as bonding, defect structure, and thermodynamic and electronic characteristics. Erbium has been studied in several previous investigations.5, 6 It was deemed desirable to more thoroughly and accurately define the system, both for the phase equilibria and the thermodynamic properties. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure hydrogen, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GM 100A and CVC, GM 110). Pure hydrogen was obtained by passing hydrogen through a heated Pd-Ag thimble. The hydrogen was analyzed and found to have only a trace of oxygen and nitrogen. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit hydrogen to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to ±1°K. An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to ±0.5 Torr and in the McLeod range (10-4 to 10 Torr) to ±3 pct. The hydrogen compositions in erbium were calculated in terms of hydrogen-to-erbium atomic ratio. These compositions were estimated to be ±0.01 H/Er. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9 pct +. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<1 vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the pressure-temperature-composition relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 grain for each loading of the reaction chamber. The procedure employed to obtain the pressure-temperature-composition data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen of erbium was wrapped in a tungsten foil capsule to prevent contact with the quartz tube. After loading the specimen, the system was evacuated to less than l0-6 Torr, flushed several times with high-purity hydrogen, and evacuated again ready for the start of the experiment. The furnace was then brought to the desired temperature. A measured amount of hydrogen was admitted into the chamber. Equilibrium was allowed to be attained, the pressure read, and the process then repeated many times until 1 atm of gas pressure was finally reached. Other isotherms were then developed in the same manner. The partial pressure plateaus were determined by another manner. In the solid solution-dihydride region a composition of approximately 1.0 H/Er was selected on the plateau. The temperature was varied throughout the range of interest. At each temperature level, equilibrium was achieved, the pressure read, and the next temperature attained. The temperature was cycled both up and down. In the dihydride-trihy-dride region, the plateaus were determined in the 473" to 651°K range only by heating to the desired temperature and not by both heating and cooling. The data were much more reproducible in this manner. Equilibrium required long periods of time. Specimens were initially hydrided to 2.8 H/Er, so that at the higher

Jan 1, 1969

By A. S. Yue

It was deemed desirable to obtain an understanding of the vacuum desulfurization process. McKechnie1 has reported that the sulfur content of nickel- and cobalt-base alloys is reduced in vacuo. Keverian and Taylor2 have observed that vacuum melting causes desulfurization of iron-carbon-silicon alloys. Garnyk and samarin3 have desulfurized transformer steel by vacuum treatment. Experiments were conducted in order to investigate the desulfurization of liquid iron under reduced pressures, and to establish the effect of some alloying elements, and various crucible materials. A vacuum-induction furnace of 50-lb capacity was used. The charge was Armco iron. Silicon was added as 90 pct ferrosilicon, carbon as electrode graphite, and aluminum as high-purity aluminum metal. Magnesia and silica crucibles were used, their inside diameters were 5 1/2 and 5 3/8 in., respectively. The temperature was measured with an optical pyrometer and it was held at 1600 1 15°C. Samples were withdrawn with quartz tubes of 6 mm ID, without disturbing the furnace atmosphere. Pressures were measured with an alphatron gage. The experimental results are shown in Fig. 1. They indicate that: 1) Sulfur can be removed from liquid iron alloys by vacuum treatment; 2) The desulfurization is enhanced by the presence of silicon, carbon, and aluminum, all these elements increase the activity of sulfur dissolved in liquid iron;4 3) The pronounced effect of silicon indicates that probably a volatile silicon sulfide is formed, Alcock and Richardson5 have observed a similar phenomenon; 4) The same rate of desulfurization was obtained when the metal was contained in either magnesia or silica crucibles. Dr. J. Keverian has contributed many discussions and recommendations. M. S. Sutliff has helped in conducting the heats. The permission of General Electric Co. for this publication is gratefully acknowledged.

Jan 1, 1960

By Lewis M. Haupt

Discussion of the paper of Mr. Granger, presented at the New Haven meeting, February, 1909, and published in Bulletin No. 25, January, 1909, pp. 1 to 37. LEWIS M. HAUPT, Philadelphia, Pa. (communication to the &apos;Secretary*) :-This subject is of great interest to me, and I am noting progress and conditions as a test of my own judgment in advocating what I believed to be the nearer, cheaper and better route at Nicaraugua. I have as yet learned nothing to change my views, or modify the convictions which led me to retire from the Commission; but that is not the issue to-day. Our government is committed to the Panama route, and is bound to " make good." There are many points presented by Mr. Granger which seem to me worthy of very serious consideration. But when all is said there remains the risk of seismic convulsions, to which either form of canal is subject; and I fail to see that the risk would be reduced by making the cut deeper, with greater surcharge of lateral pressure upon the side walls. A severe earthquake in the rainy season would doubtless close either type of canal. One of the arguments in favor of the Panama route most insisted on, was that Nature had provided good natural harbors at its termini. Recalling this, it has interested me to note that the cost of creating the necessary harbors is estimated at $27,000,000. Mr. Granger refers to this, and quotes the Board&apos;s report to the effect that, on the Atlantic side, it will require 5 miles of jetties to " make an excellent harbor out of a wretched one." The vulnerable part of Mr. Granger&apos;s paper seems to me to lie in the admission that the plant required is still in the embryonic stage, and that at least one machine should be built and tested " to demonstrate that the theoretical strains and forces work out in practice exactly as expected." This, how-

Jul 1, 1909

By H. H. Podgurski, F. N. Davis

In silver alloys containing less than 0.2 wt pet Cu. the reaction 9 + 1/2 0, = CuO(s) was found to proceed to equilibrium between 700o and 808oC. From measurements of the equilibrium dissociation pressures of the CuO at several temperatures, the differential heat of solution and the activity coeflicients for copper in silver were calculated. These values were found to be in reasonable agreement with those calculated from data appearing in the literature. A metastable "copper oxide" with an atom ratio of oxygen to copper as high as 1.7 was formed by internal oxidation at 300°C of these same dilute Ag-Cu alloys. No anomalous behavior was noted in the temperature dependence of oxygen solubility in silver. The solubility minima between 300" and 800°C reported several years ago can be accounted for, at least in part, by reactions with trace impurities, such as copper. Cold-worked siloer exhibits an enhanced permeability to oxygen. THIS investigation was undertaken because of our interest in interactions between solute and lattice defects in metals. The reason for the choice of the O-Ag system for study is the anomaly in the solubility of oxygen in silver reported by Steacie and Johnson1 in 1926, specifically that isobars between 100 and 800 Torr show solubility minima at 400°C. It was also claimed that the copper impurity in the silver was not responsible for the minima. Recently, Eichenauer and Müller2 proposed that surface adsorption might have been responsible for this solubility anomaly, but no adsorption isotherms are available to check the pressure and temperature dependence observed at the low temperatures. Surface-tension measurements on silver made by Buttner, Funk, and udin3 suggest that a considerable fraction of a monolayer of oxygen exists on silver at 922°C and at an oxygen pressure of 150 Torr. To account for the pressure sensitivity reported by Steacie and Johnson1 at 300°C, the oxygen bound to the surface at 922°C cannot be considered relevant; the existence of a surface layer at 300°C characterized by a lower energy of binding would be required to explain the effect. All of our attempts to detect an interaction of this type with surface sites have failed. In this investigation we have not been able to associate the dissolution of oxygen in silver with a dislocation interaction. Evidently, severely cold-worked silver does not contain a sufficient number of trapping -sites for oxygen. Indeed, our work shows that oxidation of trace impurities in the silver was probably responsible for Steacie and Johnson&apos;s results. In addition, we have been able to establish the nature of the reaction with copper impurity in silver by thermodynamic considerations. EXPERIMENTAL PROCEDURE Measurements of both the internal oxidation rates and the solubility were made volumetric ally in a system equipped with a gas burette, a mercury manometer, a McLeod Gage, and a mass spectrometer. The silver and the silver-alloy samples were protected from contamination by mercury vapor from our pressure gages by suitably placed refrigerated (-78°C) traps. Silica reaction vessels were employed for experiments performed above 500°C. Spectroscopically pure gases were used in this investigation. The highest-purity silver used in the solubility measurements was 99.999 pet. By chemical analysis 2 ppm of Cu were found in this silver. The two Ag-Cu alloys used in this research were made up to 0.14 and 0.15 wt pet Cu starting with 99.999 pet Ag. An unexpected source of error was discovered in the course of the work. At temperatures near 800°C silver distilled from the hot silica reaction tubes into cooler regions of our system. Although the weight loss of silver from the sample was not important in itself, oxygen was being consumed by the silver distilled into the cooler part of the system to form a stable oxide phase from which the oxygen was not recovered. In a separate experiment conducted to determine the necessary correction, losses between 0.2 and 0.3 cu cm (stp) of 0, in 24 hr were measured at 810°C. On the assumption that the flux of silver from the vessel to form Ag2O de-

Jan 1, 1964