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By D. W. Fuerstenau

THE object of this article is to point out the experimental relationship which exists among contact angle, adsorption density, zeta potential, and flotation rate data. In each of the experiments discussed in this article, the surface properties of quartz, as a function of pH, were measured in solutions to which constant quantities of dodecylammonium acetate were added. Morrow1 and deBruyn2 worked with solutions containing 4.08x10-5 moles per liter, whereas Fuerstenau3 and Seele worked with solutions containing exactly 4x10 moles per liter, but this difference is not significant. The pH of the solutions was regulated with HCI or NaOH in all cases. In each case, the addition of collector was constant, but the concentration of dodecylammonium ions decreased because of the formation of dodecylamine at higher pH values2 Contact Angles: Gaudin and Morrow1 presented data for the contact angle of quartz in solutions containing 4.08x10-5 moles of dodecylammonium acetate per liter between pH 2 and pH 10.15. Using the same captive bubble techniques, the writer measured contact angles on quartz in solutions containing 4x10-5 moles of dodecylammonium acetate per liter at pH values ranging from 9.9 to 13.2. Both sets of data are presented in Fig. 1, in which the contact angle in degrees is plotted as a function of the pH of the solution. From pH 2 to about 8, the contact angle increases slightly with increased pH, but further increase in pH causes a sharp rise in the contact angle to a maximum of about 80º. At pH values above 11.6, the contact angle drops sharply, reaching zero by pH 12.6.

Jan 12, 1957

The official Institute reports for the year 1929 were distributed in pamphlet form at the Annual Meeting, February, 1930, and were later included in Section 2 of Mining and Metallurgy, June, 1930, and thus made available to the entire membership. Membership In its report the Admissions Committee set forth the changes in membership during 1929, as follows: Total membership, Jan. 1, 1928, 8582; elected and placed on rolls in 1929, including 59 reinstatements, 509; loss by resignations in 1929, 88; loss by death in 1929, 110; loss by suspension in 1929, 37; membership at end of year not including Student Associates, 8856. Distribution of membership: Honorary Members, 16; Members, 6590; Junior Members, 38; Associates, 1041; Junior Associates, 1033; Rocky Mountain, 138; total membership, Jan. 1, 1930, 8856; Student Associates, 150; total including student associates, 9006. Treasurer's Annual Report, Year of 1929 Statement of Receipts For the year ended December 31, 1929 Dues: Arrears............................................ $ 3,501.75 Current............................................ 97,257.12 New Members...................................... 5,721.50 Advance........................................... 1,970.79 $108,451.16 Initiation Fees.................................................. 7,436.00 Magazine Receipts: Advertising Gross Receipts........................... $40,610.81 Magazine Sales..................................... 3,799.84 44,410.65 Sale of Transactions Current........................... $ 2,985. 15 Sale of Special Editions Current........................ 5,147.82 Sale of Back Transactions and Special Editions........... 4,186.93 Sale of Year Book..................................... 65.50 Sale of Authors' Reprints.............................. 2,585.40 Sale of Pins and Fobs.................................. 14.73 Sale of Technical Publications.......................... 1,451.55 Sale of Bindings...................................... 3,949.13 20,376.21 Net Interest Received: On Bank Balance and Temporary Investments......... $ 2,595.04 On Lie Membership Fund........................... 3,223.43 On James Douglas Library Fund...................... 5,425.61 On General Reserve Fund............................ 2,015.58 13,259.66 Miscellaneous Receipts........................................... 335.80 Total Receipts................................................ $194,269.48

Jan 1, 1930

By W. Bonfield

The temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of polycrystalline Cu 1.9 wt pct Be have been measured for the solution treated condition, an intermediate condition containing G.P. zones and ?' precipitate and the overaged ? precipitate condition, in the range from -58° to 200° C. A transition in micro -yield behavior and a large temperature dependence were noted for the intermediate condition, which are interpreted in terms of the interaction of glide dislocations with two differently sized zones. In comparison the microscopic yield stresses of the solution treated and overaged conditions were less sensitive to temperature variations and are satisfied by the Mott-Nabarro and dislocation bowing theories, respectively. A determination of the temperature dependence of the yield stress of a precipitation hardening alloy has provided a powerful tool for evaluation of the operative deformation mechanism. There is a marked contrast between the effect of temperature on the yield behavior of a metal containing coherent zones or intermediate precipitates, which can be "cut through" by mobile dislocations, and a metal containing a dispersion of noncoherent particles, through which dislocation "bowing out" is the dominant role of deformation.' These studies have in general been confined to single crystals, as it was considered that similar experiments on polycrystalline material did not produce good data because of the lack of sensitivity with which the yield stress could be determined. However, this objection has been removed by the introduction of mi-crostrain techniques, with which the yield stress in polycrystalline materials can be measured to a strain sensitivity of 10-6. Such measurements have not only shown that the deformation of polycrystalline precipitation hardening alloys can be examined with the same detail as single crystals, but also that some unexpected results are obtained.' In this paper the results obtained from a study of the temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of a polycrystalline Cu 1.9 wt pct Be precipitation hardening alloy (Berylco 25) are discussed. The temperature dependence of the alloy was measured for three different conditions: 1) The solution treated condition (a supersaturated solid solution of a containing ~12 at. pct Be3) which is obtained by water quenching the alloy from 800° C. 2) The condition of y' intermediate precipitate, to- gether with some G.P. zones,' which is produced after an aging treatment of 2 hr at 315°C from the solution treated condition. (The alloy was cold rolled to 40 pct reduction prior to aging to minimize grain boundary precipitation effects.)4 3) The condition with equilibrium ? precipitate structure2 which is developed after an aging treatment of 24 hr at 425° C. EXPERIMENTAL PROCEDURE Tensile specimens of gage length 1 in. and with rectangular cross section of 0.18 by 0.06 in. were prepared from the solution treated, cold rolled alloy and were either resolution treated for 1 hr at 800°C, followed by water quenching, or aged for 2 hr at 315°C and 24 hr at 425° C to produce the desired precipitate structures. The microstrain characteristics of the aged specimens were determined at temperatures from —58" to 200° C and those of the solution treated specimens from -58° to 30° C. Each temperature was controlled to ± 0.2°C, which was a level of stability sufficient to eliminate thermal expansion effects from the measurements (~1.2°C temperature increase produced an extension of 2 x 10-6 in.). The microplastic behavior of the specimens in the temperature range below 82" C was measured with a standard Tuckerman strain gage,5 while at temperatures above 82°C a modified Tuckerman gage with a reduced strain sensitivity (4 x10-6 in. per- in.) was used. A load-unload technique was used to establish values of the microscopic yield stress. The specimen was strained at a constant cross head speed of 2 x 10-2 in. per min to a given stress level, at which the total strain was measured. Then the specimen was immediately unloaded at the same rate and any residual plastic strain determined. This procedure was repeated for an increasing series of stress levels until the microscopic yield stress was established by a direct measure of the stress to produce a residual plastic strain of 2 x 10-6 in. per in. (It should be noted that, as reversible dislocation motion occurs at stresses less than the microscopic yield stress,2 the plastic strain rate at this level was not constant.) In an ideal test, the microscopic yield stress would be determined from a continuous stress-strain measurement, rather than from a load-unload sequence, in order to eliminate mechanical recovery effects.6 However, it was found experimentally that mechanical recovery was negligible in Cu 1.9 wt pct Be at small plastic strains for all the temperatures investigated, as the microscopic yield stress was independent of the number of load-unload cycles employed (i.e., the values measured for specimens subjected to different numbers of cycles was within the experimental scatter determined for specimens tested in an identical manner). Therefore, it is reasonable to consider the microscopic yield stress determined in the load-unload

Jan 1, 1969

Adams, Benjamin C., Jr., Student, Univ. of Oklahoma Norman, Okla. '36 Adams, Ernest C., Student, Univ. of Illinois 908 W. Green St., Urbana, Ill. '35 Adams, George H., Student, Colorado School of Mines Golden, Colo. '36 Adams, Robert Keller Mitchell Hotel, No. 18, Golden, Colo. '35 Afshar, Hadji Khan A., Student Box 63, Univ. Sta., Moscow, Idaho. '36 Ahrenholz, Herman William, Jr., Student, Lehigh Univ Bethlehem, Pa. '35 Alger, Robert P., Student, Missouri School of Mines & Met.Rolla, Mo. '36 Allen, Paul W., Student, Mass. Inst. of Tech Cambridge, Mass. '35 Allen, R. M., Jr., Student, Virginia Polytechnic Inst., "G" Co.Blacksburg, Va. '35 Alley, John Arnold, Student, Montana School of Mines Butte, Mont. '36 Amberger, R. H., Student, Michigan College of Min. & Tech Houghton, Mich. '35 Ambrosiani, F. Peter, Student, Michigan College of Min. & Tech Houghton, Mich. '36 Andersen, Burton Lee, Student, School of Mines, Univ. of Washington Seattle, Wash. '36 Anderson, Carlos, Student, Univ. of Oklahoma Norman, Okla. '36 Anderson, J. Wendell, Student, Pennsylvania State College State College, Pa. '36 Anderson, Joseph S. Cornelia Hotel, Ajo, Ariz. '35 Anderson, R. C., Student, Univ. of Washington Seattle, Wash. '35 Anderson, Roy A., Student, Washington State College Pullman, Wash. '35 Anderson, Willard. Student. Univ. of Oklahoma Norman, Okla. '36

Jan 1, 1936

By Reed W. Hyde

SOME information has been published on the sulphur dioxide concentration of gases from Dwight-Lloyd machines sintering lead ores but most of this relates to the customary practice in which the charge is relatively high in lead and is sintered in two passes over the machine. It is thought, therefore, that the following observations on sintering in one pass a low-lead, low-sulphur charge may be of interest. The data were obtained in sintering lead sulphide flotation concentrates mixed with minus 20-mesh oxide ore, the mixture carrying 16.8 per cent Pb and 5.3 per cent S. No returns were used because of the limited amount of sulphur available as fuel, but the mixture pelletized readily to make a satisfactorily permeable bed on the sintering machine. As there was a possibility that the SO2 might be utilized, a series of runs was made to determine the concentration of S02 in the gases at different points along the wind box, and the effect on this concentration of changes in the wind-box vacuum. Several runs each were made with vacuums (as measured in inches of water at the wind box) of (1) 2 to 1 1/3 in., (2) 4 to 3 1/2 in. and (3) 6 to 5 1/8 in. The averages of the determinations from each series are platted on the graph (Fig. I). The vertical scale shows the percentage by volume of SO2 (as determined by the Reich method), and the horizontal scale shows the time expressed as percentage of the total sintering time. Sintering was considered to be complete when no S02 could be detected in the gases. In all cases the depth of bed was 4 ½ in. and the weight of dry charge per square foot of hearth area was 45.2 lb. Other data are given in the table. The volume of gases corresponding to the several points along the wind box at which S02 determinations were made could not be measured, but has been calculated from the S02 content and sulphur elimination on the assumption that the volume is uniform throughout the sintering period. This is not strictly true, as with a given vacuum the volume will usually drop slightly toward the middle of the period and increase toward the end. However, this assumption is a reasonable approximation. Several interesting features are brought out by these data. In general, the published data on S02 concentration in sintering under ordinary conditions show a high S02 concentration in the early stages followed by a rapid decrease in concentration and with relatively little SO2 in the gases from the last half or third of the operation. In other words, the greater part of the sulphur elimination is obtained in the first third or half of the period. In these runs, the 6-in. vacuum, which approximates the usual operating condition, gives a curve that follows this customary pattern. Maximum S02 concentration is obtained 2 ½ min. after

Jan 1, 1942

By D. W. Fuerstenau

MEASUREMENT of zeta potentials is a useful tool to study the surface chemistry of minerals under flotation conditions.1,2 Because there is continued interest in this approach, the apparatus for obtaining zeta potentials of nonconducting solids by the streaming potential method is outlined here. Fig. 1 illustrates the streaming potential apparatus." The streaming potential cell or plug consists of two 24/40 standard ground joints (4) joined with a piece of pyrex tubing 60 mm long and 12 mm in diam (5). The electrodes are made of bright platinum disks 19 mm in diam and 1 mm thick through which 0.5-mm holes have been drilled (6). To the surface of each is welded a piece of 80-mesh platinum gauze. Each electrode is permanently mounted on the ends of the inner parts of the two standard joints by means of a platinum wire (7) which connects it to the tungsten seal at the end of the cell (8). For ease in cleaning and handling the apparatus, the streaming cell is fastened to the 500-ml reservoir flasks (1) by means of two 18/9 ball and socket joints (2). This particular arrangement permits passage of the solution in either direction through the plug of particles. Flow of solution can be stopped by a stopcock (3). One of the reservoir flasks has a large opening to permit insertion of either a thermometer or a pair of electrodes for measuring pH of solutions within the system. In making the experiments, the plug is filled with 48 to 65-mesh particles, but a layer of 28 to 35-mesh particles is placed at each electrode to prevent any of the finer particles from passing through holes in the electrodes. The assembled apparatus is shown schematically in Fig. 2. To eliminate CO2 from the solutions, all experiments are conducted in a nitrogen atmosphere. Nitrogen, used to drive solutions through the plug, is passed through a bottle of concentrated KOH solution to remove CO2 (9). A 9-liter ballast reservoir (10) is used to maintain a more nearly uniform pressure. A series of stopcocks controls the direction of flow nitrogen to the flasks (11). Tubes of as-carite prevent backflow of CO2 into the system (12). Driving pressure, which can be set at any desired value, is measured with either a water manometer (13) or a mercury manometer (14). Reservoir flasks have side arms for making pressure corrections for the difference in water levels in the flasks. Streaming potentials are measured by the circuit illustrated in Fig. 2. The electrodes from the plug are connected through mercury wells (15) to a reversing switch (16), which reverses the polarity of the electrodes depending on the direction of flow of solution through the plug. The streaming potential is measured with a Leeds and Northrup type K2 potentiometer (17). Proper choice of null instrument is important because Eq. 1 assumes that the current which escapes through the measuring instruments is negligible. An ordinary galvanometer cannot be used to determine the null point because

Jan 1, 1957

By C. H. Bowen

NDUSTRY needs a generally applicable means of defining average grain size and grain size distribution. Students of sediments hade explored this field, employing methods that might also prove useful in engineering problems. Before attempting to solve specific problems it is well to review the derivation of commonly used grade scales and the reasons for their selection. This aspect of the problem seems largely to have been lost, and a review of basic factors may suggest causes for failures in using size analysis data. Three facts are implicit in selection of a grade scale: 1) Most particulate mixtures are continuous distributions of sizes, and any grade scale that may be employed is an arbitrary means of visualizing that distribution. 2) For purely descriptive purposes, any grade scale, regardless of the rationality of the class intervals, will be satisfactory if it is accepted by a sufficient number of workers. 3) For analytical purposes, class intervals must be small enough to define the continuous distribution accurately. Further, where statistical studies are involved, a fixed relationship should exist between classes or grades. An argument in favor of geometrically related size grades lies in the fact that most particulate mixtures contain such a wide range of sizes that use of an arithmetic diameter scale is practically impossible. Udden, who recognized this fact in 1898,' proposed one of the first grade scales based on a regular geometrical interval. Udden used 1 mm as his basic diameter and a ratio of 2 (or 1/2) between classes. In 1922 Wentworth2 re-examined Udden's grade scale, retaining the same class interval and basic diameter, but extending the scale in both directions and renaming the classes. In 1930 (Ref. 3, p. 82) the American Society of Testing Materials proposed what is now known as the U.S. Standard fine sieve series, also based on the 1 mm diam, with a v2 ratio between sieves. This, then, is a one fourth Udden-Wentworth series in the sizes below the 4 mesh sieve. The U.S. Standard coarse sieve departs from the 1 mm base and uses inches; hence it is not a direct continuation of the fine series. The U.S. Standard series would thus seem to possess all the attributes of a good grade scale, which it is. It has a large number of classes (sieves). in fact too many for practical use in its entirety. This v2 subdivision of the Wentworth grades has led to the common use of two v2 sieve series, the half-Wentworth and the engineers' series. Geologists and sedimentologists favor the half Wentworth, or 18, 25, 35, 45 sieves, etc., whereas the engineers, preferring round numbers, utilize the other half of the U.S. Standard grade scale in the 16, 20, 30, 40 sieves, etc. The fixed geometrical ratio between classes is an advantage in statistical analysis, but the unequal classes cause some complications in calculations. This is especially true when moment measures are used. It was to simplify these calculations that Krumbein in 1934 devised the phi scale. Phi is defined as being equal to —log2 of the diameter in millimeters. Selection of logarithms to the base 2 relate the phi scale directly to the Wentworth grade scale in such a manner that the whole or fractional diameter values 2, 1, 1/2, 1/4 mm, etc., become rational whole numbers, —1, 0,1, 2, etc. Since this is an arithmetic rather than geometric series, calculations are facilitated. When the logarithm is multiplied by —1 the phi values below 1 mm become positive, those coarser than 1 mm negative. Because of its relationship to the Wentworth grade scale (and in turn to the U.S. Standard fine sieve series) it is not necessary to use the transformation equation to calculate the phi value for each individual sieve; this can be done graphically as shown in Fig. 1. It should be noted that this graph may be extended in either direction to include the range of sizes most commonly used by the individual worker. Application to Statistical Analysis Any attempt at systematically relating size analysis data to properties involves a statistical study whether it is recognized as such or not. Since this is true it would seem more logical to use measures and devices related to the general body of statistical theory. Several methods are available for studying particulate mixtures. One of the most commonly employed, and also the most often misused, is the histogram or block diagram. If its limitations are recognized and provided for, the histogram is a very useful tool. According to conventional practice, the bars of equal width are plotted and the values noted in terms of diameters, when in point of fact, log diameter is implied by such notation. Further, the histogram is sensitive to choice of grade scale and size of class interval, either of which may color the result. Grade scales whose classes are not related by fixed intervals are particularly difficult. Another basic weakness of the histogram is that it pictures a continuous distribution as a series of discrete grades.

Jan 1, 1957

By Shiou-Chuan Sun

THE presence of an excessive amount of tough froth in the flotation of minerals, particularly coals, may create trouble in dewatering, filtering, and handling. Froth is also a nuisance in many chemical industries.' This paper presents a study on the destruction of extremely tough froths with intense high-frequency sound. The data indicate that sound waves can be employed for continuous atandsoundwavescan instantaneous defrothing. A powerful high-frequency siren was used in obtaining the data. Also tested was an ultrasonorator of the crystal type with a frequency range of 400, 700, 1000, and 1500 kc per sec and a maximum power output from its amplifier of 198 w. The results, not presented, indicate that as now designed this machine is not suitable for defrothing. Although the sound generators of the magnetostriction type2,3 and of the electromagnetic type'.' were not available, it is beelectromagneticlieved they are capable of producing the required sound intensity for defrothing. The use of ultrasonics for defrothing was suggested by Ross and McBain1 in 1944. Ramsey8 reported in 1948 that E. H. Rose mentioned a supersonic device that broke down flotation froth but with low capacity. The writer has not been able to find any published literature containing practical experiments. Theoretical Considerations The mechanism of defrothing by sound is attributed to the periodically collapsing force of the propagated sound waves and the induced resonant vibration of the bubbles. The collapse of froth is further facilitated by the sonic wind and the heat of the siren. Sound waves can exert a radiation pressure'," against any obstacle upon which they impinge. When a froth surface is subjected to the periodic puncturing of sound waves, the bubbles are broken. According to Rayleigh9 and Bergmann,12 the radiation pressure of sound, P, in dynes per sq cm is given as: P = 1/2 (r+1)i/v where r is the ratio of the specific heats of the medium through which sound is traveling and is equal to 1 on the basis of Boyle's law; i is the sound intensity in ergs per sec per sq cm, and v is the sound velocity in cm per sec. In this case, the accuracy of the formula is only approximate, because a perfect reflection can hardly result from a column of froth. In addition to the radiation pressure, the propagated sound waves cause the bubbles of the froth to have a resonant vibration.'" he vibratory motion of the bubbles causes collision and coalescence, thereby weakening if not breaking the bubble walls. Sonic wind and heat were also generated." The sonic wind can exert pressure on the froth surface, and the heat can evaporate the moisture content of the bubble walls as well as expand the enclosed air. Apparatus The defrothing apparatus, shown in Figs. 1 and 2, consists of a powerful high-frequency siren, a glass or stainless steel beaker of 2-liter capacity with 12.4 cm diam and 17.1 cm height, and a metal reflector. The beaker was placed 2 in. above the top point of the siren. The metal reflector was adjusted to reflect and focus the generated sound waves into the central part of the beaker. Fig. 2 shows the crystal probe microphone used to measure the acoustic intensity and the mandler bacteriological filter employed to introduce compressed air into the beaker for frothing. The apparatus was enclosed in a soundproof cabinet equipped with a glass window. The siren, shown in Fig. 3, consists of a rotor that interrupts the flow of air through the orifices in a stator. The rotor, a 6-in. diam disk with 100 equally spaced slots, is driven by a 2/3 hp, Dumore W2 motor at 133 rps. The frequency of the siren can be varied from 3 to 34 kc. The maximum chamber pressure is about 2 atm, yielding acoustic outputs of approximately 2 kw at an efficiency of about 20 pct. The siren itself is relatively small and can be operated in any orientation. A detailed description of the siren has been given by Allen and Rudnick.11 Collapse of Froth To study the sequence of the collapse of froth, the glass beaker was partially filled with 920 cc water, 100 g of —150 mesh bituminous coal, 0.3 cc petroleum light oil, 0.2 cc pine oil and 1.54 cc Pyrene foam compound. This mineral pulp was agitated for 5 min and then aerated through a mandler filter until the empty space of the beaker, approximately 9 cm high, was filled completely with min-

Jan 1, 1952

By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

By A. M. Gaudin

THIS paper presents, with the help of colored photomicrographs, the new method of mineral identification termed "selective iridescent filming." This method pertains to the field of determinative mineralogy, which it provides with tools for: (1) phase identification, (2) solid solution analysis. The method should be particularly useful in the applied fields of: (1) paragenesis of ore deposits, (2) mineral dressing, (3) mineral synthesis and study of phase equilibria.

Jan 1, 1938

By Ernest F. Burchard

MOST of the iron ore smelted in Alabama blast furnaces is mined within Alabama, although deposits in the neighboring States of Georgia and Tennessee may be drawn upon when occasion requires. Of the four commercial kinds of iron ore, the anhydrous ferric oxide, hematite (Fe2O3) ; the hydrous ferric oxide, mostly the type commonly known as limonite (2 Fe2O33H2O) ; the carbonate, siderite (FeCO3) ; and the magnetic oxide, magnetite (Fe:3O4) ; the first two are found in abundance in Alabama, the third in less than commercial quantities, and the fourth only rarely. Both the hematite and the hydroxide are found in somewhat different forms according to their geologic environment. The Red Mountain hematite, of Silurian age, that crops out in well¬defined beds for 1.50 miles northeast-southwest and 40 miles northwest-southeast is the predominant source of ore. Only a small part of this area carries ore of commercial value; Birmingham and Gadsden are now the only centers of production. The ore is of sedimentary origin, probably altered from vast deposits of greensand mixed with calcareous, fossiliferous. marine debris. Other types of hematite not vet mined commercially are in metamorphosed rocks-red ore in slates in Columbiana Mountain and specular hematite (gray ore) in quartzite in the Talladega Hills.

Jan 1, 1938

By M. Vallée

This case study compares the actual production figures for the No. I and No. 2 copper orebodies of the Société Miniére Louvem, Val d'Or, Quebec, with the preproduction estimates and a postmortem geostatistical estimation using kriging techniques. The deposits considered are small subvertical sulphide orebodies which were mined from August 1970 to April 1973, producing 648,000 tons at 2.04% Cu versus the 1968 computed reserves of 671,000 tons at 2.51% Cu (with 20% dilution), thus showing a 25% overestimation of the copper contained. The postmortem geostatistical estimation based on the same 44 D.D.H. intersections available in 1968, shows 2.24% Cu (no dilution), compared to 3.23% Cu (no dilution) given by the conventional section method. Block by block kriging techniques were used, but within the ore contours as determined by the geologist. In this case, Characterized like many sulphide deposits by highly dispersed sample values, geostatistical kriging techniques permit a more realistic estimation of the metal contained within a given volume, than the conventional methods which overestimate it. This study has been conducted by the Mineral Exploration Research institute (IREM-MERI) for SOQUEM, and is one of the few case studies released with all pertinent data. More postmortem of this kind are required for geologists and geostatisticians to improve their methods and their "batting average".

Jan 1, 1977

By J. B. Hiskey

The hydrometallurgical application of thiourea in processing precious metal ores and concentrates has reached the development stage. This paper reviews recent technical literature covering the process development of thiourea leaching. In addition, recent fundamental contributions are discussed. Most of the interest in thiourea leaching has involved treating high grade concentrates that have sufficient value to just the use of thiourea as a reagent. An important development in thiourea technology is the addition of SO2 to the leaching solution. This procedure effectively reduces the decomposition of thiourea and eliminates the problems of passive surface layers that limit the leaching efficiency. Results for the thiourea leaching of a bulk sulfide concentrate and a residue from the autoclave leaching of a smelter flue dust are also reported. As determined by a standard bottle roll cyanidation test, the bulk concentrate was extremely resistive to cyanide leaching yielding only 16% gold and 2% silver extraction in 24 hours. Leaching with a relatively concentrated thiourea solution (1MCS (NH2)2) resulted in 83% gold and 75% silver extraction in four hours. With the treated flue dust residue, gold extraction was about 60%. Gold and silver extraction with cyanide was sensitive to both cyanide concentration and oxidizing conditions. Cyanidation resulted in 59% gold extraction and 77% silver extraction in 24 hours.

Jan 1, 1985

By G. V. Sullivan, B. E. Davis, T. O. Llewellyn

The Bureau of Mines, US Department of the Interior, conducted studies to recover phosphate from four dolomitic southern Florida deposits not currently mined. The samples contained 5.8-10.2% P205 and 1.7-4.8% MgO. Chemical analyses of sized fractions indicated that no pebble concentrate, +1.2 mm (+14 mesh) could be produced from these samples. A scheme was developed that consisted of desliming, grinding, scrubbing, and redesliming the ore to produce a flotation feed. Conventional one-step fatty acid fuel oil batch flotation tests on the samples resulted in concentrates containing 29.0-31.3% P205 at flotation recoveries ranging from 72.4 to 96.1% of the flotation feed. The MgO content of the concentrates ranged from 0.47 to 1.36%. Continuous flotation of the Manatee No. 2 sample indicated that commercial-grade phosphate concentrates analyzing 31.3% P205 and 0.55% MgO could be produced with a flotation recovery of 89.9%. The MgO content of concentrates obtained from the Manatee No. 1 and Hardee samples was 1.20 -1.36 %, respectively. Leaching with aqueous SO2 reduced the MgO content of these phosphate concentrates to 0.5 and 0.8%, but with a concomitant loss in phosphate recovery of about 10%.

Jan 1, 1985

By E. A. Devuyst, M. A. Mosoiu, V. A. Ettel

Nickelic hydroxide is an important metallurgical reagent used for precipitating cobalt from nickel sulfate solutions. Existing methods of preparation of nickelic hydroxide involve electrolytic oxidation of Ni(OH)2 or the use of strong oxidizing agents such as chlorine, ozone and persulfate. Although the oxidizing properties of the SO2 + O2 system have been known for some time, e.g., detection of SO2 and oxidation on iron in acidic solution, the application of this system for the preparation of nickelic hydroxide as a process was not considered in the past. The present paper describes a new method for chemical preparation of nickelic hydroxide which has been developed in INCO laboratories. The technique consists of reacting nickelous hydroxide suspensions with a slurry of calcium sulfite in the presence of air or oxygen. The main advantage of the process is the cost of reagents and an absence of soluble by-products (e.g., C1-). The chemistry of this process is unusual since the redox potential obtained during the reaction exceeds that of the oxygen electrode. Therefore, the effect of CaS03 is not just a catalytic acceleration of the reaction NI(OH)~ + 02. The so3= must be involved in the stoichiometry of the overall reaction producing in the initla1 phase some strongly oxidizing intermediate species.

Jan 1, 1981

By A. P. Herring, S. F. Ravitz

Manganese dioxide reacts with sulfur dioxide solution in the absence of oxygen to form manganous ion and dithionate ion, together with a small amount of sulfate ion. The effects of SO, concentration, hydrogen ion concentration, stirring speed, and temperature on the rate of the reaction were studied. If it is assumed that undissociated SO2 molecules react rapidly with MnO, at active surface sites and that bisulfite ions react slowly, an equation can be derived that satisfactorily represents the observed reaction rates. For solutions in which the reaction with undissociated SO2 predominates, reaction rates and activation energies estimated from diffusion theory agree well with those found experimentally. Manganese dioxide dissolves readily in aqueous solutions of sulfur dioxide. The nature of the dissolution reaction was first investigated by Gay-Lussac and welter1 in 1819; they identified a new oxysulfur radical, the dithionate ion, S2O6, as one of the reaction products. Since then, the reaction has become a standard method of preparing dithionates in the laboratory and one of the more promising methods of leaching manganese from low-grade ores. In the "dithionate process" developed by the U.S. Bureau of Mines2,3, manganese-dioxide ore is suspended in a solution of calcium dithionate and leached with gas containing sulfur dioxide. The manganese is dissolved and the sulfur dioxide is oxidized according to the reactions:

Jan 1, 1965

By J. O. Betterton, W. M. Spicer

The solubilities of antimony in the a and ß-forms of zirconium were determined between 750" and 1300°C. The a-phase forms by a peritectoid reaction, and the a/(a + ß) and ß/(a + ß) phase boundaries rise in temperature with in- ' creasing antimony. Impurities in the 99.95 pct zirconium were sufficient to influence the phase boundaries and the variation reported is approximate. The restricted solid solubility of the terminal zirconium phases, which is especially characteristic of this system, is thought to result from the low free energy of the Zr2Sb phase. ZIRCONIUM-antimony alloys are important in zirconium alloying studies since antimony is one of the highest valent elements which can be used to make zirconium alloys. The dilute alloys are of further interest as they have somewhat better corrosion resistance' than pure zirconium. The first investigation of the phase diagram was made by Russi and wilhelm2 who found a eutectic reaction, liquid (- 17.5 at. pct Sb) = ß zirconium (- 11 at. pct Sb) + Zr2Sb, at 1430°C'. The Zr2Sb phase was of complicated hexagonal structure, and by thermal analyses of the relatively impure alloys then available, Russi and Wilhelm found evidence for the peritectoid formation of the a-phase. EXPERIMENTAL In the present work, the phase diagram was re-investigated in the region 0 to 5 at. pct Sb and 750" to 1300°C using iodide-zirconium alloys. Details of the procedure have been described earlier. Essentially the alloys were prepared by arc casting and were then examined by the annealing and quenching method. The times of annealing varied from 1 hr at 1300°C to 30 days at 760°C. As in other zirconium phase-diagram studies1"5 the impurities in the zirconium were still sufficient to affect the results, and the experiments will therefore be described in 3 parts. The results from the first 2 parts of the work are shown in Fig. 1. Here the ß/(ß + Zr2Sb) and a/(a + ZrzSb) phase boundaries were determined with alloys made from 99.9 pct zirconium,* and cast under such conditions that the Vickers hardness of a alloys extrapolated to 95 to 110 VPN at 0 at. pct Sb. Such alloys were not suitable for investigations of the (a + ß) region, and the results shown in Fig. 1 near the (a+ ß) and (a +ß + Zr2Sb) regions were determined with purer alloys. These alloys had an extrapolated hardness range of 75 to 85 VPN and were made from 99.95 pct zirconium. A deviation from binary equilibrium occurs in Fig. 1 as indicated by the (a + ß) region of pure

Jan 1, 1959

By J. W. Hickman

INTRODUCTION MOST of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.1 In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,2 nickel,2 chromium ,2 Copper2, tungsten,3 molybdenum,3 beryllium ,4 uranium,4 thorium4 titanium5 and zirconium5 while investigations are in progress on tantalum and columbium, The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single, phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally, Examples of solid solutions which may present difficulties are MoO2 and W02, Fe3O4 and FeO-Cr2O3 since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of log10 KR for the several temperatures. [OF°R = -RT In KR 0 and-~75T = logi°KR] [?F°R] and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the values given in Table I to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium' oxide to form

Jan 1, 1948

By J. M. Markowitz

The movement of hydrogen in two-phase Zircaloy-2 under the influence of a thermal gradient was studied in specimens of cylindrical geometry. A gross displacement of hydrogen toward the cooler regions of the specimen was observed with consequent copious precipitation of 6-ztrconium (ZrH) there. The kinetics of the diffusion are analyzed and discussed. X HE temperature-gradient redistribution of hydrogen in a-Zircaloy-2 has been treated both theoretically and experimentally Hydrogen moves toward the cold side of the temperature gradient until a steady state has been established; tendency for further hydrogen movement because of temperature differences is nullified by the tendency to move in the reverse direction because of the concentration gradient. The steady state condition is described by the equation in which iV is the concentration of hydrogen at a point in the specimen corresponding to absolute temperature T, R is the gas constant,k is a constant of integration, and Q is a parameter called the heat of transport, characteristic Of the particular system. The value of Q has been determined for hydrogen in Zircaloy-2 by several investigators, using Eq. [11. There is considerable variation in the results, the cause of which has not been resolved; reported values lie in the range 3 to 6 kcal per mole. The physical situation for two-phase thermal migration is much more complex. The -phase boundary for the solubility of hydrogen in Zircaloy-2 ranges from a concentration of 25 ppm at 200°C to a maximum of about 600 ppm at 550°C.4a Thus, if the concentration of hydrogen in Zircaloy-2 is sufficiently great (>600 ppm), the specimen will be entirely two-phase, consisting of a matrix of a-Zircaloy-2 surrounding particles of zirconium hydride. At time zero, with a temperature gradient imposed, the relative amounts of hydride and a-phase in each infinite-simally thin isothermal section of the specimen can be determined from the phase diagram by the lever rule. Moreover, the concentration of hydrogen in the matrix phase varies from point to point, following the a solubility line. Over most of this temperature range (<450°C) 6 phase, Fig. 3, has a constant concentration.5 The diffusion rate toward the cold side should be governed by 1) the slope of the a solubility line and 2) the temperature gradient, The extra complication of two-phase thermal diffusion lies in the fact that migration of hydrogen would leave the a-phase concentration gradient unaffected, since it is fixed at any temperature only by the solubility; gross concentration changes would reflect only the relative amounts of matrix and hydride, which could vary continuously at every point. Migration of hydrogen out of a region would lead to dissolution of hydride, and

Jan 1, 1962

By R. D. Fisher, A. G. Metcalfe, F. A. Crossley

AN investigation of the application of magnetic stirring to the consumable arc melting of aluminum and nickel demonstrated that grain refinement could be obtained when there was sufficient stirring force. Also, it was found that grain refinement could be obtained in aluminum by alternately reversing the polarity of the current through the magnetic stirring coil. The effect of the latter was to periodically reverse the direction of rotation of the molten metal.&apos; Because of their promise, these findings were applied to conventionally cast aluminum. Shortly after this work was begun, Kondic2 reported experiments in which aluminum cast with 40° C (72° F) of superheat exhibited a grain size of 10 to 20 grains per cm2. When interrupted rotation was applied during solidification by mechanical means, a grain size of 800 to 1000 grains per cm2 was obtained. Magnetic Stirring Applied to Conventional Casting— The applicability of magnetic stirring to producing grain refinement in conventionally cast metal was evaluated in the following way. Three pounds of aluminum were cast into a clay-bonded graphite mold. The mold was surrounded by a magnetic stirring coil of 1000 turns. A direct current of 200 amp was passed through the casting by means of a graphite electrode which was immersed from the top. A current of 5 amp was passed through the stirring coil. The aluminum (1100 or 25) was superheated to 1600° F (871° C) and fluxed by passing chlorine gas through the melt for 2 min prior to casting. Two additional castings were made for comparison: 1) a conventional casting of metal superheated to 1600° F and 2) a similar casting through which 200-amp current was passed during solidification, but without current in the magnetic coil. Macrosections of these three ingots are shown in Fig. 1. Very remarkable grain refinement resulted in the magnetically stirred casting. It may be noted that the casting through which 200-amp current was passed has a coarser structure than the conventional casting. It would appear that this is due to the additional heat input generated by the current to the former casting. Mechanical Rotation Applied to Conventional Casting—A casting temperature of 1600° F was used throughout. Some 1 1/2 -lb castings rotated at 150 rpm were predominantly columnar with small areas of coarse, equiaxed grains close to the lower mold wall. Following these, a series of 3-lb castings was made. Macrosections of these ingots are shown in Fig. 2. The imposed rotational speed was 250 rpm. Turbulence or acceleration in the solidifying liquid was the significant factor. Fine grain size resulted in the material solidified during the period of acceleration of the liquid to the imposed rotational speed. When uniform rotational motion was achieved, the grain structure reverted to columnar. The final casting shown in the lower right-

Jan 1, 1962