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By R. Stauffer, S. Lindsay

"Sherritt Gordon Mines Limited utilizes pressure hydro-metallurgical techniques to recover nickel, copper and cobalt from su1phidic concentrates, mattes and various other metal-bearing materials.A brief description of the nickel refinery operation is given. In the nickel refinery process, an ammonia pressure leach is employed to treat the feed materials to dissolve the non-ferrous metals as their respective ammine complexes. The resulting leach solution goes through a series of steps which removes copper as copper sulphide and further purifies the solution prior to nickel precipitation by hydrogen reduction. The reduction end solution, containing the cobalt which was originally present in the leach solution as well as residual nickel, is treated with hydrogen sulphide. The resulting nickel-cobalt sulphide precipitate feeds the soluble cobaltic ammine process, which separates the nickel and cobalt and recovers the cobalt as a pure powder.A detailed description of the cobalt recovery process is given. Included are the various steps, comprising: acid leaching of the mixed sulphides, solution purification, ammine complex formation and cobaltous oxidation, two-stage nickel precipitation, cobalt conversion and reduction. A brief description of cobalt powder handling is included, along with typical physical properties and chemical analyses of the cobalt product. In general, the purpose of this paper is to describe the present plant practices employed in the recovery of cobalt as a by-product of the nickel refinery operations."

Jan 1, 1967

By Robert E. Barieau

General expressions for evaluating various thermodynamic properties applicable to the van der Waals equation of state have been derived. These formulas were subsequently used to evaluate various thermodynamic functions in the two-phase region. The results indicate that, for a van der Waals fluid, there is a finite discontinuity in the second derivative of the vapor pressure curve, in the second derivative of the chemical potential or Gibbs free energy at the critical point, and in the heat capacity at constant volume measured at the critical density. Numerical values are tabulated and graphs are presented for all functions calculated.

Jan 1, 1967

By Robert E. Barieau

This report gives the principles of the method used by the Helium Research Center of the Bureau of Mines when solving nonlinear-regression problems and contains the mathematical equations necessary to accomplish the following objectives: the evaluation of the parameters in such a way that the sum of the weighted squares of the residuals of an experimental observable is a true minimum, regardless of the functional relationship between the variables and these parameters; and the evaluation of all variances and covariances of the parameters by means of the usual approximation of the law for the propagation of errors.

Jan 1, 1967

By H. R. Cooper

Beginning from the point of view that process control of ore flotation can be approached by on-line analysis of processing behavior, an equation was developed which has characteristics useful for a multi-variable feedback loop. The application of this equation to optimizing control with a data acquisition system will be discussed in Part 11. OBJECTIVE OF CONTROL The purpose of developing a feedback method for concentrator control is to provide a means for determining ore processing behavior in order that data describing the ore can be used to make appropriate changes in control conditions while the ore continues to flow through the flotation circuit. In absence of simple linear relationships between pairs of variables in the flotation process, attention is directed to the need for a generalized relationship which possibly would incorporate all pertinent variables. It would be possible to apply such an equation to the control of variables in a concentrator in real time according to operational requirements as ore gradually changes in quality and processing behavior. To meet this objective, it is necessary to define relationships describing flotation performance in terms of performance variables capable of being measured on-line, either with on-line instruments and analyzers or with manual methods lending themselves to quick determination of meaningful information. Relationships derived to meet this objective form a model for the flotation process. The evaluation of flotation parameters of the ore and the execution of control on the basis of the derived information while the ore is continuing through the process would constitute a feedback control system. Data for the following control and performance variables can be made available: 1) ore feed rate, 2) collector addition rate, 3) lime addition rate, 4) pulp density, 5) assay or multiple assays in feed, tails, or concentrate sufficient for material balancing, 6) particle size distribution in flotation feed, 7) froth height, and 8) frother addition rate. Other process variables, such as flotation air input and mechanical agitation intensity, are usually not considered as control variables and were not taken into account in this analysis. Other data, such as that describing the ore, would be useful for concentrator process control. However, information of this type (such as ore hardness, grain size of the mineral, chemical species of the mineral, and ore surface properties) being not presently measurable in the on-line sense, has the effect of causing disturbances in the system which can be detected only indirectly. The process control system being sought must recognize disturbances by their effect on measured performance followed by determining control changes to compensate for them in meeting the objectives of improved performance (perhaps higher throughput, maximum return, etc.). A suitable model for the process having capability of recognizing the effects of ore disturbances should provide the means for introducing proper compensation through control changes. This would be done by processing on-line data with the model to calculate coefficients reflecting ore characteristics. This procedure can only be applied in a typical flotation system when on-line data can be processed at faster rates than the usual rate at which the ore in flotation feed takes on significantly different characteristics. For example, material balance data can be accumulated in approximately 5-min intervals using on-line X-ray fluorescence analysis. The flotation system time constant might be 15 min including grinding. Ore changes having time constants longer than 1 hr could be accommodated using on-line feedback control by this procedure. FORM OF A FLOTATION MODEL A suitable form for mathematical expression of the flotation process is an equation involving rates, when each of the components entering into the separation can be treated independently by a rate equation. A first-order, kinetic rate equation can be written on

Jan 1, 1967

Jan 1, 1967

By D. R. Uhlmann, T. P. Seward, K. A. Jackson, J. D. Hunt

microscopic ohservations on alloys of organic trzaterials show that dendrite arms can melt off under normal conditiorzs of growth. This occurs because of the interactiorz of' heat and matter fluxes during dendritic growth. The re melting occurs where the den-drite arms are joined onto the main deizclrite sterrz. Many detached crystals can be produced in this fashion. It is postulated that this remelting phenornenon occurs in metal alloys, giving rise to the equi-axed region in castings. Experiments peyformed orr castings of transparent materials support remelting as a primary source of detached crystals. Ob~ervations an equiaxed tones in metal castings are discussed in terms of this and other mechanisms. It is concluded that the partial remelting of dendrites is on important mechanisnl for producing the equiaxed regions in castings. THE freezing of a casting can be divided into three regions: a chill zone formed near the mold wall, a columnar region, and a third region, at the center of the casting, which is called the equiaxed zone. The origin of the grains that comprise the equiaxed region is the subject of this paper. We will first outline the mechanisms which have been proposed to account for the origin of the equiaxed region and discuss some recent experiments which cannot be explained by these theories. We will then present some microscopic observations of dendritic growth which have led us to conclude that the equiaxed zone in castings can arise from partial remelting of dendrites. This proposal is supported by observations on transparent castings. Finally, we will discuss several observations on metal castings which could not be explained previously, and which can be accounted for by the present proposal. Previous Mechanisms. Winegard and Chalmers3 pointed out that the molten central region of an ingot could be constitutionally supercooled, because of the solute layer at the growing interface. In this supercooled region, nucleation on particles could occur, giving rise to the equiaxed crystals. Another mechanism has also been suggested,4y5 that the nuclei originate in the chill zone then float or are carried by convection to the center of the casting, where they grow to produce equiaxed crystals. In this case, all the crystals nucleate immediately on casting, so this mechanism will be termed "big-bang" nucleation. Walker's Experiments. J. L. Walker has made observations on the solidification of nickel and Ni-Cu alloys which cannot be accounted for by either of the above mechanisms. In studying the grain size resulting from freezing of nickel at various undercoolings, walker6 found that at large undercoolings the grain size was small, due to mechanical nucleation, as discussed by walker7 and Horvay.' At small undercoolings, the grain size was large, and the growth dendritic. In Ni-Cu alloys, however, for initial undercoolings starting from just below the melting point and extending for a hundred or so degrees of undercooling, fine grains were also observed. Samples were undercooled 200 Centigrade degrees without nucleating, and were then heated 130 Centigrade degrees so that the undercooling was 70 Centigrade degrees, and nucleated. The samples had a small grain size, indicating multiple nucleation. There were no heterogeneous nuclei in the liquid which could operate at the temperature of growth. Constitutional supercooling could not have been greater than the supercooling of the initial melt, since the temperature rose as the freezing continued. walker -as also shown that a Ni-Cu alloy which can be undercooled to below its solidus will produce typical columnar and equiaxed regions when cast into a cold mold. This alloy could not reach a temperature below its solidus by constitutional supercooling. It could not, therefore, have nucleated heterogeneously. Neither the big-bang mechanism nor the Winegard-Chalmers mechanism can account for the fine grain

Jan 1, 1967

By A. Gene Collins

The Bureau of Mines undertook research to determine the bromide and iodide content of Mississippi and Alabama oilfield waters of the Tertiary and Cretaceous Period to determine genetic relationships of the ions, to determine their origin, and to determine their genetic relation to petroleum. The 280 samples were analyzed after a pretreatment to remove interferences. The iodide was oxidized to iodate and was titrated with thiosulfate. The bromide was oxidized to bromate and was determined iodometrically. A computer was used to calculate the correlation coefficients of iodide to bromide and to other ions. The other ions are sodium plus potassium, calcium, magnesium, chloride, bicarbonate, and sulfate. The mineral content of the samples ranged from 52 to 1,760 mg/l for bromide and from 2 to 65 mg/l for iodide. The mean bromide-to-chloride and iodide-to-chloride ratios were 0.0065 and 0.0002. The correlation coefficient matrix and linear plots indicated a definite bromide-to-calcium relationship for the brines investigated.

Jan 1, 1967

By Warren E. Morrison

Demand for energy in the United States in 1965 was stimulated by the continuing expansion of the economy. A gain of 5.9 percent in gross national product for the year was accompanied by a 4.4-percent rise in energy consumption. Domestic energy resources met about 93 percent of the nation's requirements. The remaining 7 percent consisted of imported fuels, mainly of crude petroleum and residual fuel oil. The major fossil fuels-natural gas, crude petroleum, and coal, in that order-contributed 96 percent of all commerical energy utilized, with the balance of 4 percent being primary electricity from hydropower and nuclear power plants. Production was up for all of the major mineral energy resources in 1965, with the single exception of anthracite, output of which continued to decline. Bituminous coal output for the year was 512 million tons; marketed production of natural gas, 16,039 billion cubic feet; and crude petroleum output, 2,848 million barrels. Among the secondary products processed from primary energy resources, the most significant gains were in coal carbonized for coke which increased 6.7 percent to 95 million tons, and in the output of liquefied gases from natural gas which rose 4.8 percent to 11,257 million gallons (268 million barrels). Within the latter category, the off? take for petrochemical feedstocks continued to rise at a very rapid pace.

Jan 1, 1967

Jan 1, 1967

By V. R. Miller

The Bureau of Mines investigated methods for testing the tensile and sheer strength of cast specimens of bulk solder and of soldered joints in order to increase the strength and extend the useful temperature range of soft solders. A spread-area test for determining the wettability of solder on copper surfaces was developed. Mannitol was used as a flux in spread tests to control spreading and to avoid plating, etching, and other side effects of regular fluxes. Data on commercial and high-purity solders obtained by these methods show more consistency than those reported by others from similar tests.

Jan 1, 1967

By R. O. Pynnonen

This publication is an analysis of reports to the Bureau of Mines of 44 fatal accidents that occurred during the operation of rubber-tired, front-end loaders in the mineral industry. The causes of the accidents, the nature of the work being performed, and recommendations for preventing similar accidents are included.

Jan 1, 1967

By R. V. Higgins

This report presents computer instructions for calculating the performance of three-phase flow of gas, oil, and water. The calculated results for an illustrative example are presented. The example is the waterflood of a reservoir containing free gas in the reservoir as a result of the partial depletion of the oil by the expansion of the gas initially in solution. The flood pattern for the example is a 5-spot.

Jan 1, 1967

By W. W. Krech, T. E. Perkins

As fractures are propagated through rocks, energy is absorbed near the extending crack tip. Apparent surface energies for several rocks have been measured by cleavage under dynamic con-ditions. At nominal crack velocities from 0.5 to 500 in (min, measurements showed that fractures propagated in discrete jumps. Calculated surface energies and moduli were relatively insensitive to nominal rate of cleavage. in another set of experiments, rocks were cleaved under high confining stresses. The rocks were submerged in low leak-off fluids which formed a filter cake on the freshly cleaved surfaces (similar to the hydraulic lracturing process). Apparent surface energies were increased substantially as the surrounding fluid pressure was increased. Moduli in bending increased significantly upon application of the first 1,000 psi but were insensitive to stress level at greater pressures. INTRODUCTION For almost 20 years, hydraulic fracturing processes have been utilized effectively to stimulate oil and gas wells. During this period, some process improvements have resulted from studies of fracture orientation, mechanics of fracturing, areas generated, conductivities of cracks, etc. Yet many questions remain concerning the conditions and pressures needed during fracture propagation. In this paper we will report additional studies of the mechanics of fracture extension. It was shown previously3 that large rock samples could be cleaved under controlled conditions so as to measure the apparent surface energy (that amount of energy absorbed per unit area of new surface created). In this paper we consider the effects of two additional factors on surface energies, viz.: (1) effect of cleavage rate and (2) effect of confining stress level. THEORY Cleavage experiments were conducted on rock samples similar to that illustrated in Fig. 1. Blocks of rock several inches wide, 2- to 3-in. thick, and up to 3 ft in length were grooved longitudinally with shallow guide slots. A crack was initiated and allowed to extend along the web as the top of the rock specimen was pulled (or pushed) apart. Auxiliary equipment permits the measurement of (1) force applied at the top, (2) separation at the top and (3) crack length. (Further experimental details will be given in the next section.) The rock beams created by the crack are considered ton be cantilever beams. The deflection (or separation of the rock beams) at any point is calculated 4,5 by the beam Eq. 1.

Jan 1, 1967

By B. E. Eakin, A. L. Lee, M. H. Gonzalez

Expeximental viscosity and density data of lour natural gases are presented for temperatures from WO to 340F and pressures from 100 to 8.000 psia. A correlation is also discussed and results reported. INTRODUCTION This investigation is one of several efforts by the authors to provide viscosity data for pure hydrocarbons and mixtures. Results of some pure hydrocarbons and their mix tures have been presented." Several predictive methods and correlations have also been reported.'," This paper presents the experimental viscosity and density data of four natural gases and confirms a correlation in a previous study. APPARATUS The viscometer was described previously. 2,6 A bank of stainless steel pycnometers was included to determine density in conjunction with the viscosity measurements (Fig. I). DATA AND MATERIALS The natural gases were furnished by the Atlantic Richfield Co. (Samples 1 and 21, the Continental Oil Co. (Sample 3) and the Pan American Petroleum Corp. (Sample 4). Table 1 shows the composition of these gases obtained by mass spectrometer analysis. The pure component viscosity data used in the correlation have been published."".'"', '" Experimental and calculated viscosity data for the natural gases are presented in Tables 2 through 5. CORRELATION Starling and Ellington"' have reported several semi-empirical expressions based to a certain extent on the theory of viscosity advanced by Born and Green.' The final expression presented by Starling and Ellingto'n is: i'. (micropoise) -- /t,, exp rX(7') p ..... (I) Eq. 1 was modified by Lee et 01." to represent mixture and pure component data simultaneously. This equation has the form: F = K exp [XpY] :.........(2) where K=- (7.77 i 0.0063M)Ti 122.4 + 12.9M +T .................(3) ' ' ' X= 2.57 + ---1914.5+ 0.0095M .... (4) Y = 1.11 -r 0.04 X ........(5) Over the pressure and temperature range studied in this investigation, this equation represents the data on methane, ethane, propane, n-butane and four methane-n-butane mixtures with a standard deviation* of ? 1.89 per cent. Density data by Sage and Lacey" were used to fit the equations. Eq. 2 gives reliable values of the viscosity of light hydrocarbons without prior knowledge of experimental viscosity values, but accurate density data must be available. Eq. 2 was used to predict viscosity values for the natural gases studied in this paper. The particular set of parameters contained in Eqs. 3 through 5 gave values that reproduced experimental data within 25 per cent. Needless to say, in using Eq. 2 better density values will give better viscosity results. However, those engineers who do not have accurate density values at hand or the time, or such facilities as a library, computer, etc. readily available, may feel uneasy in using Eq. 2. Therefore, the authors sought the easiest but by no means best density prediction method, which was reported by Kaf 30 years ago. A set of density values, which were calculated based on Kay's method, and a generalized compressibility factor chart were used to fit Eq. 2. The results are:

Jan 1, 1967

By J. Groyecki, M. Markuszewicz, J. Lassota, A. Zawada

The ratio of stable to unstable inclusions was found to ploy an essential role in the process of sccorldar-y recrystatlizalion in Si-Fe. The analysis of the free energy of inclusions in the range of heat-treatment of individual inclusions to be predicted. The effects MnS. ns inslable inclusions. were investigated. TO secure a high induction, the secondary recryslulliztt-lion associated wilh the texture is necessary. To obtain a low core loss an additional refiuing in the solid state is required. It has been found that sulfur can be more easily removed in racunm than in hydrogen and thai this process was hindered by the prescrzce of INCLUSIONS play an essential role in the development of cube-on-edge texture in Si-Fe. Their function consists in restraining the growth of primary grains up to about 900°C and in passing subsequently into solution at higher temperatures. This process is accompanied by the selective growth of secondary grains with (110)[001] orientation. The general effect of inclusions depends on such factors as the type of impurities, their amount. dispersion and stability, the conditions of diffusion in the space of lattice of metal, and the reactions at the metal/gas interface. In recent years, some of these factors were the subject of a special investigation. A positive influence of Mns, siN,' and vN3 has been established. The quantity of impurities4 and their dispersion5 have been found to be of major importance. Attention was called to the vital importance of diffusion and the conditions under which the impurities are removed from metal., It has also been demonstrated that in Fe-Si alloys by the techniques of powder metallurgy a special opportunity exists to obtain the (110)[001] type texture. 6 The aim of this work was to conduct qualitative investigations on the influence of inclusion stability on the development of cube-on-edge texture in a metal containing approximately 3 pct Si. Experiments were carried out on cast alloys and on those manufactured by powder-metallurgy techniques. The results obtained from these experiments were utilized to explain the phenomena involved and to analyze the relationships between stable and unstable inclusions and the magnetic properties of alloys. EXPERIMENTS AND RESULTS The raw materials used in these experiments were the powder of carbonyl iron with the analysis (in pct) 0.044 C, 0.01 Mn, 0.005 Si, 0.009 P, 0.002 S, traces of Cu, 0.06 Ni, 0.0015 Al, 0.03 Cr, 0.02 Mo, 0.01 Ti, 0.002 Co, traces of Pb, and the powder of silicon containing 94.14 Si, 0.003 S, 0.048 C. The powders were ground and mechanically mixed in 100-g batches. and then pressed at 9 tons per sq cm into 74 by 24 by 8 mm blocks. Sintering was carried out at 1100°C for 12 hr in vacuum (2 x lo-' Tr) or in hydrogen. In this instance the material was heated slowly and subjected to prolonged soaking at 350°, 650°, and 750 2C, respectively, to secure reduction of ferro-oxides. This was checked by making measurements of the dew point, which was found to change from -15" to -35°C after reduction. The compacts after sintering were hot-rolled to 2.4 mm, annealed at 800 C, and finally cold-reduced to 0.35 mm with intermediate annealing at 800°C at a gage of about 0.8 mm. Impurities were added in the powdered form and mixed with iron and silicon powders. Sulfur in the elemental state, electrolytic manganese, and pure aluminum oxide were employed. Besides, to obtain a material with low contents of impurities, especially

Jan 1, 1967

By J. L. Shultz

The Bureau of Mines extended its investigation of methanation catalysts. The noble metals (platinum, palladium, ruthenium, rhodium, osmium) and rhenium), molybdenum, and tungsten were tested in hydrogenations of carbon monoxide and carbon dioxide at 21 atmospheres in a temperature range between 200° and 600° C. From the 8 metals studied) 25 catalysts represent 5 catalyst types were prepared and tested. The impregnated 0.5-percent-ruthenium catalyst proved to be the most active and versatile of all the catalysts produced. Tungsten and the noble metals other than ruthenium were low in activity and usually required temperatures above 500° C for appreciable production of hydrocarbons. Molybdenum was moderate in activity, but further improvement in molybdenum catalysts seems possible.

Jan 1, 1967

By Roy L. Grant

The Bureau of Mines investigated the up-and-down method with factorial designs to determine if shorter, and therefore less costly, trial sequences could be used. Although sequences of 50 trials are usually recommended, sequences of 20 trials were arbitrarily chosen for the experiments with permissible coal mine explosives described in this report. These explosives were fired from a cannon pointed into a flammable natural gas-air atmosphere at the Bureau of Mines Explosives Research Center gallery to ascertain their safety properties. The investigation demonstrated that the shorter sequences led to useful conclusions with a reduction in cost of the experimental program.

Jan 1, 1967

By H. Kreye, E. Hornbogen

An increase in electrical resistivity during aging or after quenching from high temperatures is known in a large number of alloys. Plastic deformation of alloys in this condition leads to a decrease in resistivity. This anomaly has been called the K effect. This effect has been reported in Ni-A1 alloys by several authors.'-4 The nickel-rich solid solution y is in equilibrium with Ni,A1 (y') with CkAu structure. With this alloy it is therefore possible to produce a homogeneous solid solution as well as a coherent mixture of y and y. The changes in resistivity should be determined for these two conditions. In the present literature on the K effect no distinction is made between them, because of experimental difficulties to determine small coherent particles. In the present work transmission electron microscopy and image formation by (100) and (110) superlattice reflection of the y' phase was employed for a detailed determination of the temperature dependence of solubility of aluminum in nickel and the resulting microstructures with alloys up to 15 at. pct Al. The solubility line follows the equation indicating a smaller solubility than given in the literature at temperatures below 700°C. X-ray scattering was used to get evidence for short-range ordering in the homogeneous solid solutions.5 Parallel to the determination of the microstructure electrical resistivity was measured as a function of aging tempera- ture, time, and aluminum content, which led to the following results: 1) Resistivity increases slightly during aging of a homogeneous solid solution which was quenched from a high temperature as a consequence of short-range order, Fig. 1, curve c,. 2) Resistivity shows a maximum during aging of all alloys which are heterogeneous according to the phase diagram, but which were obtained as a supersaturated solid solution by quenching, Fig. 1, curve c,. The increase in resistivity is mainly due to coherent precipitation of y'. In Fig. 2 the effects due to short-range order pN and due to precipitation of particles APT are shown for an aging temperature of 450°C and different aluminum contents. 3) The increase in resistivity depends on the size !f the coherent particles. A critical diameter of 15 5A for the maximum was found for all alloys and aging treatments by extrapolating particle sizes determined by electron microscopy. 4) The maximum of resistivity of the heterogeneous conditions does not occur if particles, larger than the critical size, have formed already during quenching. 5) Plastic deformation destroys short-range order as well as small coherent particles. Therefore a decrease in resistivity is observed if the increase in resistivity caused originally by these phenomena is

Jan 1, 1967

By C. N. Rosenecker

The power required to circulate a gas-solids suspension was determined using a centrifugal compressor and a closed system. The suspension consisted of 18- to 40-micron glass beads in a mixture of 89 percent N2 and 11 percent CO2 at 20 psig. Solids-to-gas (S/G) ratios w re O to 2.2 lb/lb; gas flow rates were l.2 to 2.5 lb/min. Power requirement was found to follow the relationship hp t = hp(. + l), where hp t = the total power, and hpg = the power required for pure gas.

Jan 1, 1967

By E. K. Kleespies

The rate of the heterogeneous reaction between titanium-oxygen solid solutions and titanium trichloride in molten sodium chloride was determined at high temperatures. In the alpha phase, the reaction rate decreases uniformly with the increasing concentration of oxygen. The gamma crystalline form of titanium (above 33 atomic percent oxygen) was much less reactive than the alpha phase, and the reaction rate approached zero at 50 atomic percent oxygen. The activation energy for the reaction of titanium-oxygen solution containing 22.8 percent oxygen was 11.7 kcal/mole of TiCl3 as compared with 8.3 kcal/mole of TiCl3 for pure titanium.

Jan 1, 1967