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By J. H. Wernick

IN a study of the rate of decomposition of ½ -in. cubes of limestone, dolomitic limestone, and dolomite in a sweeping nitrogen atmosphere, Joseph, Beatty, and Bitsianesl found that the zone of calcination advanced at substantially a constant rate at a given temperature. The purpose of this paper is to show that their data indicate at least two processes occurring when the above carbonates decompose. It is suggested that there are two processes occurring temperature range and the other the limiting process over another temperature range. The data of Joseph and co-workers have been extended by use of the Arrhenius equation, Eq. 1, a relation beween the velocity constant k of a reaction and the absolute temperature T.

Jan 7, 1954

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-'. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.' and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner's3 data for cation self-diffusion, D:, using Wagner's theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner's data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-' at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By George Mah, Charles Wert

Internal-friction peaks caused by diffusion of oxygen and nitrogen have been observed in ytterbium. They are thought to be caused by the redistribution, under stress, of strain dipoles around an interstitial oxygen or nitrogen and a neighboring substitutional impurity. With the use of a simple geometrical model, diffusion coefficients for oxygen and nitrogen between special interstitial sites have been calculated. a) APPLICATION OF INTERNAL FRICTION TO MEASUREMENT OF DIFFUSION RATES IN DISSOLVED INTERSTITIAL ATOMS In bcc metals, the interstitial atoms occupy the centers of cube faces (0, 1/2, 1/2), or their equivalents, the center of the cube edges (0, 0, 1/2). An interstitial atom in this position causes an aniso-tropic distortion in the lattice. When stress is applied, mechanical relaxation can take place by the movements of the interstitial atoms. This relaxation has been used to obtain information concerning the movements of the interstitial atoms in the bcc metals. Data for these alloys have been compiled by Stanley and Wert. Other researchers have extended the investigation of interstitial diffusion to the close-packed metals. Gupta and weinig2 found an oxygen peak in a titanium, the height of which is linearly dependent on the oxygen concentration. They assumed, therefore, that they were dealing with movement of atomic ally dispersed oxygen in titanium. KG and wang3 determined that the diffusion coefficients of carbon in fcc steels and in nickel obtained by internal-friction methods were consistent with those obtained by macrodiffusion methods at much higher temperatures. Bisogni found oxygen and nitrogen peaks in hafnium by use of which he deduced the diffusion coefficient of these gases in hafnium. He observed further that the half-widths of these peaks corresponded almost exactly with those of a single-relaxation process; he assumed it to be caused by movement of atomically dispersed oxygen and nitrogen. From these studies, the deduction can be drawn that, in general, diffusion data can also be obtained for the interstitial diffusion in close-packed metals (or more precisely, in slightly impure close-packed metals). One group of such metals for which little data exist for the diffusion of dissolved oxygen and nitrogen is the rare earths. They have great affinity for gases, which enter solution interstitially. In this investigation results were obtained for the Yb-O and Yb-N interstitial solid solutions with traces of substitutional impurities; these solid solutions are of fcc structure. b) MECHANISM OF THE RELAXATION IN FCC CRYSTALS In the fcc structure, an interstitial gas atom is usually situated in the octahedral position (1/2, 1/2,

Jan 1, 1964

By A. F. Bertuzzi, M. R. Tek, F. H. Poettmann

A method is presented for predicting pressure drop for two-phase fluid flow in horizontal pipes. A set of 267 experimental measurements randomly sampled from approximately 1,000 measurements from various literature sources was used. Pressure gradients calculated by the procedure developed and compared with the experimental values showed a bias of +0.82 per cent and a standard deviation of 20.8 per cent. The advantatges of this method over other available methods of predicting two-phase flow pressure drop are (a) its comparative simplicity of application, (b) its relative independence of flow patterns, (c) its accuracy, which on the basis of a statistical evaluation predicts pressure drop closer than other available methods, and, (d) its ability to satisfactorily correlate laboratory data from various sources while the correlations from these sources do not appear to agree with one another. The method has been reduced to a simplified graphical procedure, suitable for field use. A two-phase f factor is defined and correlated with parameters involving the flowing gas-liquid mass ratio, a Reynolds number for the gas phase, and a Reynolds number for the liquid phase. The choice of parameters allows the correlation to reduce to the usual f factor plot for the limiting conditions of (111 gas or all liquid. INTRODUCTION The mechanics and characteristics of two-phase flow systems have been of interest throughout the industry for some time. In numerous engineering installations such as pipe lines, chemical reactors, and heat exchangers, two-phase flow conditions are of every day occurrence. In oil production operations it has been desirable, in some cases, to consider transporting gas and oil together in a common pipe from oil field to process plant. The trend toward centrally located stock tank batteries in oil fields has resulted in longer gathering pipelines in which more than one fluid phase is flowing. The increase in the producing capacity of oil wells due to new production tech- niques has created the need for review and re-design of many surface gathering lines for properly handling the increased production. Optimum pipe size for the situations described above has become an important factor. The problem which is of interest here involves the ability to predict the relationship between pressure drop, fluid properties, fluid rates, pipe diameter, and pipe length. Although the literature1,5,10,13,18,19 contains various articles dealing with specific cases of the problem, Lock-hart and Martinelli17 proposed the most general solution. Their method has been later modified by Baker:1 Alves2 demonstrated that different flow patterns are possible for a flow mechanism defined by Martinelli such as gas turbulent, liquid turbulent. Baker explained deviations experienced with Martinelli's correlations on the basis that different flow patterns could exist for the same flow mechanism. Using Martinelli's method of correlatioil, Baker correlated data for each flow pattern for the turbulent-turbulent flow mechanism. Bergelin and Gazley6,7 presented a correlation for predicting gas phase

Jan 1, 1957

By Paul A. Beck, John Towers, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350' to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.' Fig I shows a log D vs. log t plot of French's data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French's data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.' Walker's specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker's data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949

By John Towers, Paul A. Beck, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350' to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.' Fig I shows a log D vs. log t plot of French's data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French's data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.' Walker's specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker's data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949

By A. U. Seybolt

In part 111' of this series it was shown that during the selective oxidation of a 3 1/4 pct Si-Fe alloy in damp hydrogen, only silica, (observed at room temperature) as low cristobalite or low tridy-mite or both, was formed as an oxidation product. In some in- „ stances where the film was fairly thin (probably well under 100A) there was some suggestion of an amorphous form of SiO2. The present investigation of oxidation rate showed that the selective oxidation of silicon-iron can be rather complicated, and apparently impossible to rationalize in an unequivocal manner. In some temperature regions, notably near 800" and 1000°C, the data seem to obey the familiar parabolic rate law. However, at intermediate temperatures complications were noted, some of which are possibly due to the order-disorder reaction in the silicon-iron solid solution. IN an earlier report' it was shown that during the oxidation of 3 1/4 pct Si-Fe alloys in H2O-H2 atmospheres only silica films were formed in the temperature range from 400° to 1000°C in hydrogen nearly saturated with water at room temperatures, or at dew points as low as -45°C. In the work to be reported here, some observations are made on the rate of oxide film formation. As in the earlier investigation, electron diffraction patterns generally showed either low tridymite or low cristobalite or both, except for some very thin films. These sometimes showed diffuse rings, presumably due to a very small crystallite size, or in a few cases, diffuse bands probably caused by an amorphous film. EXPERIMENTAL PROCEDURE Vacuum-melted silicon iron made of high-purity materials was rolled into strips 0.014 in. thick, and cut into samples 1/2 in. wide by 1 in. long. Chemical analysis showed 3.2 pct Si and 0.002 pct C. All samples were surface abraded with 600-grit paper, were solvent cleaned, and then placed in an paper,apparatus containing a "Gulbransen type"2 micro-balance. Here the gain in weight of the samples of about 5 sq cm area could be followed as a function of time during the oxidation caused by the water in atmospheres of various controlled water-hydrogen ratios. The water-hydrogen ratios can most easily be described as varying from a dew point of 0°C (PH2O-p^2 = 6.2 x 10-3 , to K (P j -40°C (PH2O/PH^= 1.3 X 10-* Most of the experiments were conducted at the 0°C dew-point atmosphere because drier atmospheres caused so little gain in weight that the accuracy of measurement was poor. Because of this, only the data obtained at PH2O,/P,,,= 6.2 x X3 will be reported. The temperature range extended from 800" to 1000°C; and most of the oxidation runs lasted for about 24 hr. The reproducibility of any reading was about ± 1 ?, but the sensitivity of the balance was about 0.2 ?. The atmosphere, flowing at 200 cm per-min, was preheated to the furnace temperature before contacting the specimen. While the gas flow caused a measurable lift on the sample, it was ordinarily sufficiently constant so that it was not an appreciable source of error. X-ray and electron diffraction checks of the samples before and after oxidation showed no evidence of preferred orientation, either on the metal samples or on the silica films formed. EXPERIMENTAL RESULTS The data obtained are summarized in Table I, and some are given in detail in Figs. 1 to 4. In the fourth column of Table I, kp refers to the parabolic rate constant in the expression (?/cm2)2 = kpt + c [1] where ? = micrograms gain in weight kp = parabolic rate constant in units r2 /cm4 t = time in minutes c = constant It will be noted that in many cases no value for kp is given; this is because in these instances the data did not obey the parabolic rate law. The silica film thicknesses given in the last columns are values calculated from the weight gain, an average tridy-mite-crystobalite density, and by assuming a perfectly plane surface. Fig. 1 shows the data plotted in the form of Eq. [I], hence a linear plot indicates parabolic behavior. It has been frequently observed in the literature that

Jan 1, 1960

By J. H. Wright

Longhole sublevel stopes excavate ore with which the production geologist has only remote contact; therefore, predicting grade and tonnage from such a stope can be a problem. However, the longholes themselves yield data that can be used to improve those predictions. Here, a radial distribution method of weighting sample data is discussed, which is useful in forecasting grade and tonnage from certain longhole sublevel stopes.

Jan 1, 1985

By B. Post, D. Moskowitz, F. W. Glaser

Lattice parameters of various hafnium compounds, two borides, a carbide and a nitride were determined. Some physical properties were measured and comparisons with the properties of the corre-sponing zirconium compounds were drawn. A LTHOUGH borides of transition metals have A been extensively investigated in recent years, there are few references in the literature to borides of hafnium. This is not surprising, in view of the extreme scarcity and great cost of the purified metal. Becker' reported the existence of a boride, carbide, and nitride of hafnium; he listed the formulas as HfB, HfC, and HfN. However, in his work no mention was made of chemical analyses of the reaction products. In this paper results of a study of various hafnium compounds, including borides, carbides, and nitrides, are reported. It was expected, of course, that these compounds would closely resemble their zirconium analogues, which have previously been extensively investigated. Three borides of zirconium are known: ZrB,² ZrB,² and ZrB212.4 In addition, one carbide, ZrC,5 and one nitride, ZrN,5 have been reported. It should be noted that ZrB and ZrB12 are stable phases only in relatively high-temperature regions, unlike ZrB2, which is stable from room temperature to its melting point." It was felt that hafnium would yield corresponding borides, carbides, and nitrides with similar stability ranges. Experimental Procedures and Results A quantity of hafnium metal that was better than 97 pct pure, with zirconium as its major impurity, was furnished by the Argonne National Laboratories. The boron powder used was approximately 96.5 pct pure. In general, the procedure involved mixing the metal and boron powders in the desired proportions, and subsequently hot pressing them. The resulting specimens were analyzed chemically and phases present were identified by X-ray diffraction methods. A Philips Norelco Geiger counter spectrometer was used for identification of components and for measurement of lattice constants. Filtered copper radiation was used for all X-ray work. Electrical resistivity and density measurements were carried out at room temperature. The stable diboride, HfB2, will be described first. Stoichiometric quantities of boron and metal were heated to approximately 2000°C during hot pressing. The reaction product was shown by X-ray diffraction methods to be isomorphous with ZrB2 (space group Dlgh; P6/mm). Values of lattice constants of HfB2 compared with those of ZrB2 are shown in Table I. The calculated density of HfB2 is 11.2 g per cc, compared with a measured (pycnometric) value of 10.5 g per cc. HfB2 specimens prepared under a wide variety of conditions (including variations in initial Hf-B ratios) showed only insignificant variations in lattice constants, indicating a very narrow range of homogeneity. Like ZrB2,7 HfB2 is an excellent electrical conductor. The resistivity at room temperature of hot-pressed samples, approximately 85 pct dense, is 12 microhm-cm. This compares favorably with the electrical resistivity of 10 mi-

Jan 1, 1954

By K. R. Janowski, A. B. Chase, E. J. Stofel

Ruby crystals of exceptional optical quality have been grown from fluxes composed of Bi2O3 + PbF2 or Bi2O3 + BiF3. Careful control of growth conditions was required to minimize the number of growth defects consisting primarily of dislocations, occluded flux, and growth twins. Slow growth rates coupled with the addition of small amounts of La2O3 as a flux dopant were helpful in producing nearly perfect crystals. Chromium concentrations up to 1 pet were incorporated into these crystals without adversely affecting their perfection. Crystals up to 10 mm in diameter having as few as one to ten dislocations per crystal were typical of those produced under optimum growth conditions. Under these same conditions the occlusions were eliminated, and growth twins were either eliminated or reduced to one to three twin boundaries per crystal. INTEREST in the nature of lattice imperfections produced during the growth of ruby crystals (Al2O3-corundum structure) has been stimulated recently by the need for ruby lasers of good optical uniformity. As a result, ruby crystals grown by the flame-fusion (Verneuil) process have been studied in detail and have been found to contain high densities of dislocations (106 to 107 dislocations per sq cm) and mosaic structures that impair their optical quality.'-3 Attempts to improve the quality of Verneuil-grown crystals by controlling the growth variables have not been entirely successful. On the other hand, rubies grown by the flux process have received little attention even though their more nearly equilibrium growth conditions suggest that they would have fewer growth defects. Nelson and Remeika have shown recently that small flux-grown rubies can indeed be made into very low-loss lasers. However, they did not report information on crystalline imperfections in these crystals.4 Stephens and Alford have reported briefly on defects found in a flux-grown corundum crystal but they neither described these defects in detail nor related them to the method of growth.5 The present investigation was undertaken to establish the relationship between growth conditions and crystalline perfection of flux-grown rubies, sapphires, and other crystals of the corundum family. EXPERIMENTAL PROCEDURE The corundum crystals used in this study were grown by slowly cooling solutions of A12O3 in molten-salt solvents of PbO + PbF2, Bi2O3 + PbF2 or Bi2O3 + BiF3. The materials employed were Linde A (a Al2O3 powder) with reagent-grade chemicals as solvents. Some of the solutions also contained small additions (1 pet or less) of one or more of the transition metal elements chromium, manganese, iron, and titanium as crystal dopants. La2O3 was added to some of the solutions to alter the growth habit of the crystals. The La2O3 promoted the occurrence of growth facets parallel to (0112) and {1011} planes, where the indexing system is the morphological system described in detail by Kron-berg6 and used throughout this paper. The melts from which the crystals were grown were prepared by mechanically mixing the various constituents and placing them in platinum crucibles. The covered 50- and 100-ml platinum crucibles were heated in muffle furnaces at 1250°C for short periods of time (1 to 4 hr) and then program-cooled at either 2° or 4°C per hr to 1000°C. At this lower

Jan 1, 1965

By Karl F. Peterson, H. K. Najarian, Robert E. Lund

PRIMARY products of the Josephtown smelter are zinc metal of various grades, lead-free zinc oxide pigments, cadmium metal, and sulphuric acid. Zinc concentrates of domestic and foreign origin are blended and desulphurized at the roaster plant. The equipment includes five, 12-hearth Herreshoff roasters and two modified Trail-type suspension roasters. The sulphur dioxide containing gases from the roasting operation are diverted to a four-unit contact acid plant for the manufacture of sulphuric acid. The roasted calcines are agglomerated by sintering on Dwight-Lloyd-type sintering machines; the sinter is crushed and sized within required limits; and the sized sinter is smelted in vertical shaft-type electro-thermic furnaces. Of the 13 electrothermic furnaces of various sizes now in operation, four are designed to produce American process zinc oxidc of various specifications; and the remaining nine furnaces are equipped with vacuum-type condensers and produce zinc metal. Papers describing the general smelting practice at Josephtown have been published by AIME. Since both High Grade zinc metal and lead-free zinc oxide pigments are produced direct from the electrothermic furnaces without need for subsequent refining, the elimination of impurities such as lead and cadmium has to be accomplished during roasting and sintering operations. To effect the producing of both High Grade and Prime Western zinc products, the roasting and sintering operations are on two separate circuits. A High Grade circuit produces finished sized sinter low in lead, cadmium, etc., for the High Grade furnaces; and the Prime Western circuit produces finished sinter destined for the furnaces producing Prime Western metal. Sintering at the Josephtown smelter differs in many important respects from the sintering practice in smelters operating horizontal retort zinc furnaces. Requirements of the electrothermic smelting furnaces define the physical characteristics of the sinter, while the chemical composition of the sinter is controlled according to the grade of metal and oxide to be made as final products. Three principal objectives in the sintering process at Josephtown smelter are: 1. To transform the zinc calcine from the roasting operations into a hard, yet porous agglomerate that will not crumble in the smelting furnace. 2. Crushing and sizing of the sinter to obtain a proper screen analysis which is normally —% in. down to +1/4 in. particle size. 3. To eliminate, particularly in the High Grade circuit, as much of the impurities such as sulphur, lead, and cadmium as possible. The sintering plant as originally built in 1930 was equipped with three standard 42 in. x 44 ft Dwight-Lloyd sintering machines. Each machine was equipped with a 15x60 in. sintering corporation fan driven by 150 hp, 900 rpm synchronous motor through a magnetic clutch and capable of delivering 30,000 cfm of air at 15 in. of water and 150°F. Each sintering machine was driven by 7½ hp dc motor with controllers for varying the speed of the machine from 8 to 32 in. per min. The pallets were cast iron and the grates of the herringbone type. The charge was mixed in a 4 ft diam x 8 ft Stehli pugmill and transported by belt conveyor, elevator and tripper conveyor to a small bin over each machine. Shortly after the start of operations the following changes were found necessary: 1. The herringbone grates which plugged very quickly and were difficult to keep clean were replaced by straight, narrow cast-iron grate bars running at right angles to the travel of the pallets. These grate bars are held in place by a center bar extending across the pallet on the 24 in. dimension and by removable retaining plates which form the sides of the pallets. 2. Mechanical grate knockers were developed in conjunction with new grate bars for continuously and automatically cleaning the grates. 3. As the cast-iron pallets cracked, they were replaced with cast-steel pallets. In 1938, the capacity of the sinter plant was increased with the installation of two 42 in. x 22 ft machines which were brought from the company's Herculaneum lead smelter. With a circulating load of some 250 to 300 pct, production of finished sinter on the 42 in. x 44 ft machines at this time amounted to about three tons of sized sinter per machine hour. In 1945, one of the 42 in. x 22 ft machines was replaced by a 60 in. x 44 ft machine of our own design. In 1948, as part of the plant-wide expansion program, the sinter plant not only was expanded but also divided into two separate plants; namely, Prime Western and High Grade circuits. The sinter destined for furnaces producing Prime Western zinc metal is made in a new plant comprising two 60 in. x 44 ft Dwight-Lloyd-type sintering machines, each having a 45,000 cfm Sturtevant fan at 18 in. water static pressure and served by an 8 ft diam x 12 ft long rotary charge pclletizer and auxiliary crushing and sizing equipment. The sinter destined for furnaces producing High Grade zinc metal and zinc oxide pigments is produced in the old sinter plant which was expanded to accommodate four of the 60 in. x 44 ft sintering machines, replacing the old sintering units. In the High Grade sinter circuit, two units of the 60 in. x 44 ft machines are used as preliminary soft sinter machines; and the remaining two units of the 60 in. x 44 ft machines are used to make finished hard sinter. Purification Theory Partial elimination of lead and cadmium in the sintering of zinc ores is common knowledge. However, by some manipulation and by taking advantage of the double circuit, it is possible to make zinc sinter which is nearly free of contaminators. Lead

Jan 1, 1952

lv. H. Blauvelt, Great Falls, Montana (communication to the Secretary): In his remarks on Mr. Stetefeldt's paper (Trans., xxiii., 587)) Mr. Goetz observes: " Trouble experienced with producers at Great Falls influenced me to try Taylor producers instead of those of Wellman. But recent reports show that the Wellman producers work better, besides coating nearly 50 per cent. less than Taylor producers of equal capacity. Indiana and Illinois coals cannot be used in the Taylor producers by reason of the large size and hardness of the clinkers which they form." I think that Mr. Goetz must have been misinformed regarding the work of this producer in Illinois. One of the large mauafacturing concerns in that State, the Illinois Zinc Company, situated at Peru, which uses a coal mined in the vicinity, tried one Taylor producer, some four years ago, in competition with those of an older type, which it had been using. As a result of this trial, the company has now thirteen Taylor producers, which have been in operation for about three years. A recent report from these works says that the Taylor producers have largely reduced the loss of coal through the grate, and have also improved the quality of the gas, as compared with that produced from the same coal in the producers of the older type. This Illinois coal is, perhaps, the worst in the country for making gas; since, besides containing from 20 to 40 per cent. of ash, it carries a large quantity of pyrites, so that the clinkers are large and extremely hard, and the capacity of the producer is most severely tested.

Jan 1, 1895

By A. E. Jenkins, L. A. Baker, N. A. Warner

Rates oj decarburization of levilated Fe-C droplets conlaining 5.5 to 0 pct C have been measured at 1660°C. Gas mixtures of 1, 10, and 100 pct 0, with helium diluenl were used at velocities of 12.5 and 62.5 cm per sec. Rates were independent of carbon concentration in the mell and in good agreement with the calculated rule of oxygen diffusion through the gas boundary layer. The effects of flow rale and total pressure are as predicled and the rates are approxitnalely 2.5 times those with CO2 as oxidant. The mass-transfer correlation used incorporaled the efject of natural convection as well as forced conrection. Graphile spheres are shown to oxidize at the same rate as Fe-C droplets under the same experimental codlions. It is concluded that, for high carbon concentrations in the melt, the rate of- decarburizalion is controlled wholly by the rate of gaseous diffusion. Rate measurements with pure CO, are reported for low carbon concentrations where CO bubbles nucleate within the droplet. Under these circumstances the decarburi-zation decreased with carbon concentration and it is proposed that carbon diffusion is significant in conlrolling the decnvburization rate. In an earlier paper1 decarburization rate measurements were reported for levitated Fe-C alloys at 1660°C but with CO2 as the oxidant. The decarburization rate was found to be independent of carbon concentration in the melt but slightly affected by total pressure. The authors were unable to explain the slight pressure effect but in all other respects the results were consistent with control by diffusion in the gas boundary layer. Subsequent work has been directed at finding the reason for the slight pressure effect and whether the kinetics with oxygen as oxidant parallel those with CO2. Recently Ito and Sano2 have shown that with water vapor-argon atmospheres the decarburization rate is gaseous diffusion controlled until an oxide film appears on the surface. In this work the melts were contained in crucibles. MASS TRANSFER IN THE GAS PHASE In the earlier analysis1 only forced-convection mass transfer was considered. Subsequent recognition of the existence of some free-convection mass transfer explained the observed small effect of total pressure on the decarburization rate. Steinberger and Treybal3 and Kinard, Manning, and Manning4 have developed correlations involving the linear addition of the contribution of radial diffusion, free and forced convection. Steinberger and Treybal&apos;s correlation was chosen as the most applicable to the present work since it correlated most of the data available in the literature and handled the low Reynolds number region exceptionally well. The correlation for (Gr&apos;Sc) < 108 is where Nu&apos; is the Nusselt number for mass transfer based upon the total surface of a sphere in an infinite medium, G&apos; is the mean Grashof number for mass transfer defined by Eq. [2], Sc is the Schmidt number (µ/pDAB)f, Re is the sphere Reynolds number (dpu,pf/µf), p is the viscosity of the gas (poise), p is the density of the gas (g cm-3), Dab is the binary diffusivity for the system A-B (sq cm sec-&apos;), dp is the sphere diameter (cm), u is the approach velocity of the gas (cm sec-I), and subscript f denotes the property value is computed at the film temperature Tf defined by Tf = +1/2(To + Tr) where To is the specimen temperature and T, is the approach gas temperature (oK). Natural convection occurs when inhomogeneities exist in gas density. These may be caused by concentration gradients, temperature gradients, or both. In the present work the temperature gradient between the sphere and the bulk gas was very large and in some cases, for example the runs with pure oxygen, the concentration gradient was also appreciable. The Grashof number defined by Mathers, Madden, and piret5 was used since it took account of both temperature and concentration gradients: where Gr&apos; is the Grashof number for mass transfer (p2fgd3|-yA-yA|/µ2f), Gr is the Grashof number for heat transfer (p2f gd3p|To - T,]/µ2fTf), Pr is the Prandtl number (cpµ/k)f, g is the acceleration due to gravity (cm sec-&apos;f, a is the concentration densification coefficient (1/p)(ap/ayA)T, yA is the mole fraction of component A at the gas-metal interface, yA is the mole fraction of component A in the bulk gas stream, cp is the heat capacity of the gas per unit mass at constant pressure (cal g-I OK-&apos;), and k is the thermal conductivity of the gas (cal cm-&apos; sec-1 OK-1). Mathers et al. tested this combined Grashof number

Jan 1, 1968

By G. P. Gladis, R. H. Atkinson

PALLADIUM has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items-at least 100 times as rare as gold. Although both visual and spectrophotometric examination demonstrated that the color of palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400° to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By M. R. Goldick

THE Roan Antelope concentrator was originally designed with a nominal milling capacity of 6000 tons of copper ore per day but this was subsequently considerably exceeded. In broad outline the plant consisted of two No. 30 McCully gyratory crushers for coarse crushing, five 5 1/2-ft Standard Symons crushers in open circuit for secondary crushing, ten No. 98 Marcy ball mills arranged in five sections, each two-mill section with primary and secondary Dorr classifiers for two-stage grinding. One stage of flotation roughing was followed by two stages of cleaning, all in airlift type pneumatic flotation machines, with the final concentrates filtered on Oliver drum filters. Tailing was thickened in a 250-ft Dorr traction type thickener before pumping to the tailing dam. Concentrating operations commenced in June 1931, on the completion of the first two ball-milling sections and output was increased during the next few months as the remaining sections were finished. From the start, very few technical difficulties were experienced but a number of evolutionary changes have been made as a result of operating experience and the availability of improved equipment. These have resulted in plant and ore-flow alterations although the general scheme of ore treatment remains substantially as before. The main changes to date were the installation of a new crushing plant at Storke shaft, some 7000 ft west of the original Beatty shaft; the completion of a two-stage secondary crushing plant; an increase of 20 pct in ball-milling capacity; a change-over from pneumatic to a mechanical type of flotation machine for flotation roughing; the reduction of flotation cleaning from two stages to one stage. ORE TREATED Typically the ore treated consists of metamorphosed shales and sandstones with shales as the principal mineral-bearing rock carrying chalcocite, bornite and chalcopyrite as the main copper minerals. Chalcocite predominated in the original eastern end of the ore body but there is a pronounced trend to an increased proportion of the copper-iron sulphides as mining proceeds westward. Although the ore can be described as soft, this advantage is offset by the extremely fine dissemination of the copper minerals which calls for a high degree of comminution of the ore (90 pct minus-200 mesh Tyler standard) to give a reasonably satisfactory separation of mineral from gangue. Latterly, there has been a tendency for the ore to become harder as shown by a reduction in the ball-milling rate from a previous figure of over goo tons per ball-mill day to the present output of some 800 tons. Chalcopyrite is not so finely disseminated and has also proved more amenable to flotation than chalcocite. Nonsulphide minerals are mainly the so-called oxides such as malachite, cuprite and melaconite with some chrysocolla and

Jan 1, 1947

By A. H. Geisler, J. H. Keeler

Preferred orientations in unalloyed zirconium were determined by the Geiger-counter spectrometer X-ray diffraction technique. With increasing P-annealing temperature the following textures were obtained: l—a retained a-annealing texture, 2—additional orientations predictable from the a-p (Burgers) relationship, and 3—a texture derived from a cube texture in the p phase. Earlier work on cold-worked and a-annealed zirconium was reappraised to show a quantitative dependence of rotations on temperature and to identify spurious areas of some of the pole figures. IN a previous paper,&apos; the preferred orientations of high purity zirconium sheet were described for cold-rolled and annealed samples. Annealing temperatures up to 900°C, which is slightly above the allotropic transformation temperature, were explored. Of interest was the observation that the orientation of the hexagonal-close-packed material after annealing in the temperature range of the stable body-centered-cubic phase was similar to that of the material which had been annealed in the a temperature region, although a change in texture would be expected because of the many new orientations based on an orientation relationship between the two forms of zirconium. The reversion to an original orientation after an allotropic transformation cycle is not unusual. It has been found for titanium,"* for thallium," and for cobaltB among the hexagonal metals. Burgers found in his original work7 that, when zirconium was cooled through the allotropic transformation and then reheated, the body-centered-cubic phase reverted to the original orientation. Additional experimental work has been carried out to further explore the textures of zirconium after annealing in the temperature range above the allotropic transformation. In addition, a reappraisal was made of the earlier results for zirconium&apos; in light of recent work on titanium4 which has shown that the texture type depends quantitatively on the temperature of annealing and that spurious areas may be encountered in the pole figures of hexagonal metals determined by the X-ray spectrogoniometer technique of analysis. Experimental Procedure Crystal-bar zirconium prepared by the iodide process was the material used in this investigation. The major impurity was hafnium which was less than 0.3 pct. The composition obtained by spectro-graphic analysis is given in Table I. Cold-rolled specimens were prepared from crystal bar by a series of reductions of approximately 0.010 in. until the sheet reached a thickness of 0.010 in., after which it was cold rolled to 0.001 in. thickness between sheets of alloy steel. The total cold reduction amounted to about 99.8 pct. Specimens were annealed for % hr at 1000" to 1100" to 1200°C or 1 hr at 1400°C in an evacuated Vycor or quartz tube. The transmission pole figures were obtained by

Jan 1, 1956

By Stephen G. Dardaganian

Pore volume compresibilitieu measured in the laborutory on core .samples are reported for typical reservoir .sarrrl.rtorres at reservoir pressure. These cornpressibilities ore different for each reseriloir sample and cannot be correlated to porosity. The compressihilities are a1so functions of presslire. In recent years several authors have pointed out the importance of including pore volume compressibility of the reservoir rock in certain reservoir engineering calculations. Hall&apos; showed that in calculating the hydrocarbon volume of an undersaturated reservoir from the production per unit change in reservoir pressure, the neglect of rock compressibility could, in the extreme case of low porosity rock, lead to results in error by a factor of two. Hawkinsl&apos; and Hobson and Mrosovsky showed that both rock and interstitial water compressibilities must be included to achieve satisfactory accuracy in this calculation. Although rock compressibility is an important reservoir property in these calculations, very few data are available. Hall&apos; made compressibility measurements on a few samples in a small pressure range. No other direct pore volume compressibility measurements have been reported. Geertsma&apos; discussed the elasticity of reservoir rock but did not present any new data. In this paper, rock compressibilities suitable for reservoir calculations are reported for a variety of sandstones typical of U. S. reservoirs. The measurements were made through a range of pressures which is also typical of reservoirs. EXPERIMENTAL PROCEDURE Plugs 1 in. in diameter and 2- to 3-in. long were diamond drilled, 14 from cores from seven oil-bearing or potentially oil-bearing sandstone, one from a quarried sandstone, and another from a shallow, oil-free, pure orthoquartzite. The plugs were extracted in toluene, vacuum dried, and then weighed. The plugs were then saturated with kerosene and reweighed. This gave pore volume. They were then again extracted in toluene. vacuum dried, and jacketed in 0.004-in. thick copper foil. A short length of -in high pressure tubing led from the jacket. The jacketed sample was then saturated with kerosene and placed in the hydraulic pressure cell as shown in Fig. 1. Movement of the mercury slug showed the change in pore volume of the sample under a given pressure change. Temperature was about 72" F for all measurements. Before taking any measurements, the external pressure on the sample was raised to 10,000 psig and kept there for several hours. This formed the thin copper jacket around the plug. 7-he pressure was then removed and the sample left at least overnight, during which time it recovered its original pore volume. An external pressure of 12,000 psig was then applied and held constant. The change in pore volume was noted as the internal pressure was raised in 1,000 psig increments to 10,000 psig. The internal pressure was then reduced to zero, again noting pore volume changes,

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,&apos; 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&apos;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&apos; 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 J. B. Seabrook

The accompanying Fig 1 is a graphical scheme of intermediate accuracy for expediting interconversions of mol, weight, and volume percents. This chart consists of a family of curves of mol or atomic or volume percent plotted against weight percent, each curve in the family providing for a certain ratio of molecular or atomic weights or densities. Thus, the whole range of variations is presented in a very familiar format, and the conversion is effected simply by choosing the proper curve and reading off the required values. An entire series of conversions for a given binary system can be found by following the appropriate curve. It is interesting to examine the analytical geometry of the plots. The curves, which must fit into a square and all join at the 0 and 100 pet points, may be shown to be hyperbolas with their centers on the extension of the diagonal of the square which they intersect. Multiplying out the expression x A atomic fraction of A = y = ------ where x is the weight fraction of A, and A and B are atomic weights, we get xy+A/By- A/Bxy=x Upon rotating and translating axes and avoiding imaginaries, it is found that the angle of rotation is —45°, the origin moves upv2/2 units andv2/2(A/B+1/A/B-1) units to the right, and the standard form is Thus the curves are equilateral hyperbolas, their centers are units away from their intersection with

Jan 1, 1950