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By Henry Leidheiser, Melvin C. Jr. Hobson

The rate of formation of the intermetallic compound, indium antimonide, at the interface between iudium and antimony at 100°C is greatly increased when a composite electrode of indium electrode -posited on antimony is made the cathode in an electrolytic cell. The amount of indium antimonide formed during electrolytic treatment at constant potential appeared to he proportional to the square root of time, but the scatter of the data, particularly at long times, makes it impossible to state this conclzlsi1:ely. The rate constant for the electrochemical synthesis was estimated to he 1.5 x 10-12 sq cm per sec. A similar- set of experiments was conducted in the absence of an applied potential but under otherwise similar conditions. The rate constant lor the thermal synthesis was less than 2 x 10-14 sq cm per, sec, at least two orders of magnitude less than obtained during electrolytic treatment. In a series of electrochemical studies it was observed that intermetallic compounds formed on the surface of polarized electrodes.1'2 The possibility of using this technique for the electrochemical preparation of intermetallic compounds was investigated and subsequently applied to the synthesis of the semiconducting III-V compounds. Gallium antimonide, indium arsenide. indium antimonide, and indium bismuthide were successfully formed by electrodepositing the Group III element from a boiling acid solution onto an electrode made of the Group V element. The following kinetic studies were undertaken on indium antimonide to obtain quantitative information on the rate of formation of this representative III-V compound under a potential gradient. EXPERIMENTAL The electrolytic cell for these experiments was a modified, three-neck, round-bottom, 500-ml distillation flask. Sealed into the side of the flask was a Luggin probe which monitored the surface of the working electrode and extended out of the flask to a small reservoir containing a saturated calomel electrode. The counter electrode was platinum. The three electrodes were connected to a Wenking po-tentiostat which maintained a preselected constant potential near the surface of the working electrode with reference to a saturated calomel electrode. All potentials noted in this paper are with reference to a saturated calomel electrode at 45° ± 5°C. The potential and the current were both monitored using Sargent Model MR recorders. The antimony electrodes were cast in graphite molds to form spheres about 15 mm in diameter with a shank 6 mm in diameter and 10 mm long. A heavy copper wire (12B & S gage) was soldered to this shank. Collodion was applied for protection to the shank and the connecting part of the copper lead. A snug-fitting O-ring was slipped over the shank and the electrode was then fitted into a teflon holder such that only the spherical portion was exposed. The electrode surfaces were cleaned and chemically polished prior to assembly and introduction into the electrolyte by etching in a modified CP-4 solution (50 parts glacial acetic acid, 10 parts concentrated nitric acid, 2 parts 48 pct hydrofluoric acid). The electrolyte was 10-2 M In+3 in 1 MH2So4 and its temperature was held constant by refluxing. The reflux condenser was open to the atmosphere and no temperature correction was made for changes in barometric pressure. The indium concentration in the electrolyte was checked from time to time by the analytical method outlined below for the determination of the amount of indium antimonide formed electrochemically. A schematic of the recorded potential is shown in Fig. 1. At point A the antimony electrode was introduced into the cell and the open-circuit potential recorded. At point B the potentiostat, preset at the desired potential, was switched on. It was switched off at point C and the potential fell to the open-circuit value of the electrodeposited indium. The

Jan 1, 1965

By M. S. Moats, C. M. Campbell

Samples of a high impurity (90.05 wt. % Cu, 4076 ppm Pb, 1939 ppm As and 635 ppm Bi) commercial copper anode were characterized and then electrorefined in a laboratory scale cell. Anode inclusions were examined using backscatter mode scanning electron microscopy and energy dispersive spectroscopy. Hundreds of inclusions were measured for size, morphology and composition. Commonly found inclusions were copper oxide (Cu2O), complex oxides (Cu-Pb-Bi-As-O) and copper selenides/tellurides. The weight percent of lead and arsenic increased with increasing inclusion size up to 4- 5 microns. During electrorefining, starter sheet ductility was negatively impacted by thiourea addition. The importance of arsenic (V) concentration on the electrolyte concentration of bismuth was observed. INTRODUCTION Copper electrorefining is a commercial process used to produce the majority of the world’s refined copper. During this process, impure copper anodes are dissolved electrolytically, and high purity copper is deposited on cathodes. As the anodes dissolve, the impurities either accumulate in the electrolyte or report to solids that form on anodes surfaces or at the bottom of the refining cell. These solids are called slimes. Slimes contain precious metals and are collected for further processing. Slimes are also an important outlet for problem impurities such as lead, antimony and bismuth. The electrorefining process is operated in such a way to encourage the deportment of these elements to the slimes. Impurities in copper anodes have been studied extensively by Chen and Dutrizac (1990, 1993 and 2005). The most common impurities found in modern copper anodes include: Ag, As, Au, Bi, Fe, Ni, O, Pb, Sb, Se, Sn and Te. Impure copper anodes are produced by pyrometallurgical methods and have purities ranging from 97.7–99.7% Cu (Moats et al., 2019). The composition ranges of commercial copper anodes from the 2019 worldwide tankhouse survey are given in Table 1. The concentrations of anode impurities vary widely dependent on the source material and prior processing steps. Based on the work of Chen and Dutrizac, both gold and silver are predominantly found in solid solution within the copper grains while a minor amount of Ag can be found in Cu2(Se/Te) inclusions. Nickel is entirely soluble within the copper grains up to anode compositions of 2500–3000 ppm Ni; above which NiO and kupferglimmer phases are formed (Chen & Dutrizac, 1990). As, Bi, Pb and Sb are found in solid solution within copper and within oxide inclusions typically found along grain boundaries. Oxides are formed due to the presence of 0.13-0.18 wt. % O (Chen & Dutrizac, 1990). This is because during solidification of the cast anodes, impurities are enriched in the liquid phase as the copper grains nucleate and grow. The inclusions form from the last liquid to freeze, which is typically along grain boundaries (Wenzl & Filzwieser, 2007; Wenzl, Filzwieser, Mori & Pesl, 2008).

Jan 1, 2019

By R. S. Wagner, H. Brown

Criteria for nucleation with the aid of twin planes during crystal growth from the melt are discussed. It is shown experimentally that bismuth crystals can grow from a subercooled melt in a twinned bismdtic form. A mechanism of growth based on the presence of at least me twin plane is proposed. It is well known that faceted growth can be observed in crystals grown from the vapor phase, dilute solutions, or from the melt. Faceted growth, in which the crystal is bounded by its slowest growing faces, will occur if the growth rate is strongly orientation dependent. The addition of atom layers on a facet plane can only occur by two-dimensional surface nucleation or with the aid of an imperfection. Nucleation with the aid of dislocations was proposed by rank' and observed to be of particular importance in crystal growth from the vapor phase. Nucleation with the aid of two-dimensional imperfections, notably twin planes, was suggested by stranski2,3 and Frank.4 A twin plane, terminating at the growth interface, can form a reentrant step at which nucleation can occur at a much smaller super-saturation (or supercooling) than required for two-dimensional surface nucleation. Nucleation by a twin plane usually results in a fast growth rate along a crystallographic direction parallel to the twin plane. Such a nucleation mechanism, based on the presence of a twin plane, has been used by Dawson5 to explain the growth and morphology of sheet-like crystals of paraffin n-hectane. In recent years more evidence was found that nucleation by twin planes occurs frequently in crystal growth from the vapor phase and from dilute solutions, for example, in cadmium,' barium titanate,7 silver,8 silicon9 and gallium arsenide.10 In crystal growth from a supercooled melt, however, nucleation by twin planes has so far only been observed in materials with the diamond or zinc blende structure. Bennett and Longini11 were the first to recognize the important role a single twin plane plays in the growth of germanium dendrites. Subsequently, it was found that a prerequisite for continued propagation of germanium dendrites is the presence of two parallel twin planes which form a self-perpetuating system of nucleation sites.12 Sili- con and some III-V compounds such as InSb also grow dendritically by twin plane nucleation. It appears that the following criteria must be satisfied in order that nucleation with the aid of twin planes can occur: A) The growth form of the material must be faceted." B) The formation of twin boundaries, by a fault in layer sequence during growth, by plastic deformation, or by an accidental meeting of properly oriented crystals, must be possible. C) Twinning must form a reentrant step where the twin boundary terminates at the faceted growth interface. D) These three conditions are necessary, but in certain cases not sufficient for continued crystal growth with the aid of a twin plane. Depending on interface morphology, a combination of more twin planes is sometimes required to form a self-perpetuating system of nucleation sites. This investigation was carried out with the idea in mind that nucleation with the aid of twin planes is a more general phenomenon and should occur in those materials, grown from a supercooled melt, which satisfy the criteria outlined above. It has been found that crystals of high-purity bismuth grown from a supercooled melt can grow by the aid of a twin plane. In the first two sections the faceted growth form and the twinning elements of bismuth are discussed. In the last section prismatic crystals of bismuth, which appear to grow with the aid of a deformation twin are discussed.

Jan 1, 1962

By W. P. Diamond

The direct method test was developed for general mine safety applications by the U.S. Bureau of Mines in the early 1970's to measure the gas content of coal samples obtained from the relatively shallow depths of eastern U.S. coal mines. Over time, applications for gas content data evolved which required increasingly accurate desorption values. It became evident that some of the inherent weaknesses in the original direct method test could best be addressed by abandoning the water displacement based desorbed gas volume measurements. The ideal gas law based modified direct method (MDM) and associated desorbed gas volume measurement apparatus was developed to provide the most accurate desorption values possible for rock samples obtained from any gas-bearing strata. The MDM has a number of significant advantages, including: (1) increased accuracy, especially for low gas content samples, (2) a test apparatus with an integral sampling port to facilitate the collection of uncontaminated gas samples, (3) an inherent head space effect correction in the periodic MDM desorbed gas volume calculations, (4) measurement of positive and negative desorbed gas volumes, (5) elimination of differential gas solubility effects as a source of error inherent in the water displacement methods, and (6) a compact and rugged test apparatus that along with the elimination of the ?glassware? required for the water displacement methods, facilitates its use in the field.

Jan 1, 2008

By Philip W. Holland

The U.S. Bureau of Mines has developed an improved method for determining dissolved helium in water in the concentration range of 4.0 x 10-8 to 270 X 10-8 cm3 He (STP)/cm3 H2O. The method is a modification of a previously reported method that was developed for analrzing surface and subsurface waters in geochemical survey work. Water samples are collected in SOD-cm stainless steel cylinders, and the dissolved gases in a sample are extracted into an evacuated cylinder of equal volume. After addition of 30 psig of nitrogen containing less than 2 ppb helium to the extracted gases, the resulting mixture is analyzed for helium using a helium-tuned mass spectrometer. The helium content of the water sample is determined from an empirical calibration that is established by analyzing standard solutions of helium in water. The accuracy of the method is ±7 pct for helium-in-water concentrations above 10 x 10-8 cm3 He (STP)/cm3 H2O.

Jan 1, 1989

By A. L. Jamieson, H. Rosenthal

The action of mercury on stressed brass to produce cracks was known before Moore, Beckinsale and Mallinson1 showed that actual season cracking did not occur spontaneously but could be induced by ammonia. These investigators studied other substances, including diphenylamine, without finding that anything other than ammonia could cause season cracking Grimston2 reported season cracking in cartridge cases stored in wooden boxes wetted with dilute sulphuric acid pickling solution. Season cracking associated with sulphur dioxide, water vapor and air has been reported by Johnston,3 although he reported that trimethylamine and pyridine did not cause cracking. Jevons4 has ascribed season cracking of brass in certain instances to trimethylamine, "aldehyde amine," "ketone amine" and pyridine, but no experimental work was done evidently to prove this definitely. Pyridine was investigated by Morris,5 who found it to have considerable cracking power. In the present investigation, the object was a qualitative evaluation of a number of representative amines with respect to their ability to cause season cracking. Thus it was desired only that an appreciable vapor pressure of each amine be obtained in order to make the test as severe as possible, without attempting to test equivalent concentrations for comparative purposes. MEthods Specimens TWO types of specimen were used: 1. Unannealed 70-30 brass CUPs formed from 0.040-in. thick sheet. Height of cup Was 13/8 in. and diameter was 17/8 inches. 2. First draw pieces of caliber .50 cartridge cases in the unannealed condition (70-30 brass)- The cups were representative of a thin wall and thin base specimen, whereas the draw pieces have a thick base (1/4 in.) and a thick wall (approximately 3/32 in.). Both types of specimens contained high residual stress and cracked in less than one minute in a solution of I per cent mercurous nitrate and I per cent nitric acid provided that this was receded by a 30-sec. pickle in 40 per cent nitric acid. Specimens were prepared as follows: (1) degreased in trichlorethylene, (2) rinsed in H2O, (3) pickled 5 min. in 10 per cent by volume H2SO4 (1.84 SP. gr.), (4) rinsed in H2O, and (5) dried. Amirtes Tested In selecting the amines, representatives of the three series of amines, and one series of substituted amines were chosen. The aliphatic series was represented by the methyl and ethyl primary, secondary and tertiary amines. These are the simplest aliphatic amines. For the aromatic series, the phenyl primary, secondary and tertiary amines were selected as being the simplest. The heterocyclic series was represented by pyridine, which is a simple heterocyclic base (tertiary amine).

Jan 1, 1944

The 1997 Rapid Excavation and Tunneling Conference (RETC) was held at the Mirage Hotel, Las Vegas, NV. The RETC is a biennial event jointly sponsored by SME and the American Society of Civil Engineers (ASCE). Conference attendance was 573 members, nonmembers and students, an increase of seven attendees from the 1995 conference in San Francisco, CA. Exhibitors occupied 51 booths at the Las Vegas RETC. The 1997 conference encompassed 58 presentations in 15 sessions. Participants were given details on achievements and advances that have resulted in new design solutions, alternative work practices and increased productivity within the industry. The page at the end of this article tells how to get your copy of the RETC proceedings, either hardbound or on CD-ROM. Or, if you wish, for the first time a CD-ROM is available with the complete RETC proceedings from 1972 to 1997. This two-disk, archival volume has key-word search capability, is in portable file format and is compatible with PC and Macintosh platforms. RETC program sessions included design and planning, ground support, tunnel boring machine (TBM) case histories, conventional excavation, new technology, difficult ground, geotechnical, shafts and raises, future/special projects, new Austrian tunneling method, international projects, soft ground case histories and water and gas. What follows are highlights of some of the RETC presentations.

Jan 1, 1997

By Arthur. H. Winckers, Stephan L. Chryssoulis

"The deportment of gold in residue samples of cyanide leach tests of David Bell ore from level 6A block 13 was established using a comprehensive quantitative mineralogical approach. In every test the feed was first pre-aerated for 4 hours, followed by 48h cyanidation. Test no. 2 was done without lead nitrate and yielded a residue assaying 3.03g Au/t. In test nos. 4 and 9 lead nitrate was added before pre-aeration at 0.03kg/t and 0.3kg/t respectively yielding residues of 1.04 and 0.81 g Au/t.The mineralogical approach employed to establish the deportment of gold involved superpanning, to preconcentrate the free gold and assaying of the tailing fraction to determine the gold associated with quartz. It was thus determined that without lead nitrate added 47.2% of the lost gold is in the form of residual free gold particles less than 20 µm in size. It is this form of gold which is under represented in the residues of leach tests with lead nitrate added.Having eliminated coarseness of gold particles as a factor for lower recovery, it was determined that the residual gold particles have extensively contaminated surfaces. Amongst the deleterious surface contaminants identified: S, As, Ag, Sb and Hg, the two most harmful are S and Hg because of their concentration on the surface and rate of accumulation.Mercury and Ag are minor constituents of native gold at David Bell (average composition Au: 78.9 wt%, Hg: 18.5 wt% and Ag: 2.6 wt%) and they become enriched on the surface of residual gold particles because of their slower rate of dissolution in cyanide. The other elements absorb onto the gold particles from solution.The beneficial effect of lead nitrate was documented by comparative surface analysis of gold from residue samples of 48 hour leach testing with and without lead nitrate added and from time dependent (0-2 hour) leach tests in the presence and absence of lead nitrate. Lead nitrate accelerates the dissolution of gold by performing the following functions: (i) catalytic effect on the cyanidation of gold by accepting electrons; (ii) reaction with surface sulphur to form PbS which is then removed by oxidation; (iii) catalytic reaction on amalgam and Ag facilitating the cyanidation of Hg and Ag thus slowing down their build up onto the dissolving gold particles and (iv) the precipitation of sulphide sulphur from solution thus minimizing its build up on the surface of dissolving gold particles which is believed to facilitate the access of cyanide ions."

Jan 1, 1996

By J. B. Cheatham

An analysis of indexing is given for an idealized plastic rock. Indexing refers to chipping from a bit tooth to a previously formed crater. A method is indicated for computing the dependence of chip size and shape as well as force on the tooth for various tooth shapes as a function of crater configuration and distance to the previous crater. Pressure on the tooth is found to vary with depth of penetration after a critical depth has been reached. Damp sand model experiments indicate that simple solutions using linear and logarithmic spiral slip-line fields for Coulomb plastic materials give reasonable approximations to the failure patterns. Both idealized roller cone bits and fixed blade or drag bits are considered, and methods are presented for approximating the force on the bit and the chip volume when the rock is subjected to sufficiently high pressure to behave plastically. One of the primary objectives of drilling research investigations is to develop theoretical equations which can be used to predict the behavior of rock under drilling loading conditions. Since rocks usually fail in a brittle manner at atmospheric conditions, much current research is directed to studies of the brittle failure of rock under the action of drilling too1s. 1,2 The results of triaxial test on rocks indicate that both rock strength and ductility increase at high confining pressures.3 Recent results from single bit-tooth indentation experiments on dry rocks indicate that the transition from brittle to ductile failure under a bit tooth can occur at pressures sufficiently low to be of interest in oil well drilling.4 Single bit tooth experiments and analyses are not directly applicable to the drilling process since one of the important facets in drilling is the interaction between a bit-tooth and the previously formed crater. This interaction is referred to as indexing.' The purpose of the present paper is to indicate how plasticity theory can be applied to the analysis of indexing for plastic rock. Drag bit or fixed-blade drilling is considered and a discussion is given of the drilling action of an idealized roller cone bit. Results of simple experimental studies using a damp sand model are given as a method of visualizing the failure patterns in rocks under high confining pressures. These results are compared with plasticity theory using simple solutions based on linear and logarithmic spiral slip-lines. Discontinuous stress fields are proposed for drag bit drilling based upon the soil mechanics analysis of Shields. SINGLE BIT TOOTH RESULTS Single bit tooth indentation experiments using dry rocks under pressures from 0 to 5000 psi have indicated a correlation between the shape of a force-displacement curve and the nature of the rock failure beneath the tool.4 Continuous linear curves are in-

Jan 1, 1965

By Martin Hertzberg

The concept of limit burning velocities, formulated in an earlier Bureau of Mines report (RI 8127), is applied to the problem of flame propagation through tubes of finite size. The limit burning velocity for conductive-convective wall-loss quenching (process b) is (Su)b = [aPe,] where the proper choice of critical Peclet constant, Pe, is determined mainly by the ratio of contact-perimeter loss area to flame-zone cross sectional area. This ratio of loss area to propagation area relates to the shape of the flame front and its control by buoyancy and by boundary conditions. The comparison of (Su)b with previously defined limit velocities for systems mixed by natural convection allows one to assess the influence of tube dimensions and boundary constraints on the "true" or earthly limits for the three directions of propagation. The flame quenching caused by inert powders is shown to be similarly described in terms of a limit burning velocity, (Su)?b. The tube's surface-to-volume ratio (~1/ro) is simply replaced by the powder's surface area per unit volume of the flammable mixture. Thermal loss quenching by these "internal walls" occurs at a critical Peclet constant somewhat higher than that observed for tubes, and the problem is complicated by the finite heat capacities of the powders and particle lag effects in the flame front.

Jan 1, 1980

By George A. Grandy, D. W. Fuerstenau

Simulation of nonlinear grinding systems is discussed in the context of the size-discretized batch-grinding model. A linear approximation of environment-dependent (or nonlinear) selection functions is postulated for systems which exhibit feed grinding orders less than unity. For this, a convex linear combination of zero and first-order selection function forms is used to obtain an analytical solution that can be used for simulation. An example in which marked nonlinear behavior occurs is rod-mill grinding. Accordingly, a series of grinding experiments was carried out in a batch laboratory rod mill to test these techniques; agreement between experiment and the model was found to be very good. Recently, significant progress has been made in the simulation of linear grinding systems by using a population balance mathematical model. Herbst and Fuer-stenaul presented a parameter estimation scheme that can be used with the size-discretized batch-grinding model, and Gumtz and Fuerstenau3 have extended these techniques to the simulation of locked-cycle grinding. Grandy et aL." summarized the simulation of linear systems and noted important alternate solutions to the batch-grinding equation. Kelsall et a1.'-" discussed the dynamic simulation of linear batch grinding, as well as linear open and closed-circuit grinding. In all of these, the key word is linear, which certainly restricts the engineer trying to simulate a variety of grinding systems. This paper discusses an approach for the simulation of non-linear grinding systems, particularly those which exhibit grinding orders less than unity. Experimentally, dry rod-mill grinding is used to evaluate the technique presented. Batch Grinding Model The size-discretized batch-grinding model has been discussed in detail by Mika et al.'.' and by Herbst and Fuerstenau,' and therefore, will only be briefly developed here. The model is formulated by making a differential mass balance of each size fraction in such a manner that the equation parameters are precisely defined in terms of selection and breakage functions,' which can be either calculated'.' or estimated1 from experimental data. The model is phenomenological because it averages all stress-application events in the system and, therefore, does not distinguish the manner in which individual particles are stressed.' For this average environment, the resistance of all particles in a size fraction to breakage is defined by that size-frac-tion's selection function; and when fracture occurs from an average event, the breakage product size distribution is defined again by that size-fraction's breakage function. The model is deterministic and is derived in terms of a continuous time variable and a discretized size variable,' i.e., the n mass fractions associated with the n defined size intervals (see Table 1 for nomenclature).

Jan 1, 1971

By H. L. Paterson, R. R. Keays, M. J. Donaldson, D. J. Boyack, M. F. Smith, J. J. Gresham

"Albite-rich sedimentary rocks that contain abundant Fe sulphides occur in the lower portion of the ultramafic sequence at Kambalda and their broadly antipathetic relationship to most of the nickel orebodies is well documented. These sediments generally contain less than 0.1% Ni, but nickeliferous equivalents with 0.3 to >6% Ni occur locally in close spatial association with more typical volcanic peridotite-associated massive, matrix and disseminated ores. Nickeliferous sediments have been mined at several locations at Kambalda but, collectively, they constitute less than 2% of the total Kambalda nickel reserve. The nickeliferous sediments occur both on the ultramafic-footwall basalt contact and within the lower part of the ultramafic sequence, and are usually less than 5 m thick. They are commonly finely laminated rocks with a cherty appearance, composed essentially of layers of albite+quartz±amphibole, alternating with pyrrhotite+pentlandite±pyrite layers. Some contain a minor amount of carbon. The sediments are only of ore grade (> 1% Ni) immediately adjacent to massive Fe-Ni-Cu sulphides, which are interpreted as normal magmatic ores on the basis of geochemistry and the presence of distinctive ferrochromites. The nickel content of the sediments decreases to background levels (<0.1%) within about 20 m of the massive sulphides. In most locations the massive sulphides clearly have been emplaced tectonically within or adjacent to the sediments, which are commonly highly deformed. Typical nickeliferous sediments contain about 1% Ni, 0.1% Cu, 0.1% Zn, 400 ppb Pd, <0.2 ppb Ir and 10-200 ppb Au. They have lower Ni/Cu (average 10), higher S/Ni (average 6) and higher S/Se (average 11 200) than associated massive sulphides (average 40, 4.8 and 7400, respectively). The Pd/Ir ratio of the nickeliferous sediments (typically > 1000) contrasts markedly with that of associated massive sulphides (average ca 16).The high Pd/Ir values are similar to those which have been reported for hydrothermal Fe-Ni sulphides and barren sulphidic sediments of probable volcanic exhalative origin. They preclude a direct magmatic origin for the sulphides in the nickeliferous sediments, though S/Se and S isotope data indicate a magmatic source for the sulphur. The restriction of nickeliferous sediments to within about 20 m of normal magmatic sulphides and the lack of a widespread Ni dispersion halo suggest local redistribution of originally magmatic Ni. This probably occurred by diffusion and hydrothermal mobilization during deformation and amphibolite-facies metamorphism. Although not totally ruled out, a volcanic exhalative origin for the Ni seems unlikely."

Jan 1, 1984

By Jack C. White

The Bureau of Mines, in its efforts to insure the continued viability of the domestic minerals economy, has been engaged for several years in research on the extraction of alumina from domestic, nonbauxitic resources. Hydrochloric acid leaching of kaolin is one of the more promising technologies being studied for recovering alumina for feedstock to existing aluminum smelting capacity; 93 pct of this feedstock is currently imported either as bauxite or alumina. Organics contamination of pregnant leach liquor, originating during solvent extraction for removal of iron from aluminum chloride solution formed during hydrochloric acid leaching, causes rapid deterioration of the semihard rubber lining of process equipment. These organics were removed by a skimming tank-coalescer-activated carbon adsorption system. Organic levels of less than 10 ppm from the coalescer and less than 0.5 ppm from carbon adsorption were achieved. Analytical methods employing CC14 extraction and infrared spectrophotometry were developed to determine the organic content of both the liquor and the carbon. Mass transfer zones delineated in the carbon columns provide adsorption data for the design of larger systems.

Jan 1, 1981

By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors&apos;-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By Dale R. Ralston, Roy E. Williams, Gerry V. Winter, George L. Bloomsburg

Ground water inflow into a mine and the re¬sultant impact on district hydrology can be pre¬dicted on a site specific basis once the ground water flow systems at the site are sufficiently well under¬stood so that a valid conceptual model can be de¬veloped. Ground water flow systems are controlled by the hydrogeologic properties of the materials at the, site, including hydraulic continuity along flow paths, and boundary conditions. Preliminary delin¬eation of hydrostratigraphic units for conceptual models frequently can be based on surface water data; specifically, spring locations and the gain-loss reaches of streams. Quantitative predictions of mine water inflow and its impact on regional hydrology require col¬lection and analysis of numerous types of data. Hydraulic conductivity must be defined quantita¬tively both parallel and perpendicular to bedding as well as areally for each hydrostratigraphic unit. The characteristics of the Davis shale in case his¬tory number 2 illustrate this concept very well. The storage characteristics also must be determined for each hydrostratigraphic unit and the potential or hydrostatic head should be quantified vertically and areally for each unit. The potentiometric measure¬ments in the Bonneterre Formation as discussed in case history number 2 illustrate this point. The data collection and data analysis techniques constitute the weak link in the analysis of mine inflow and district impact. The technology for char¬acterizing a mine site in the field has lagged behind the technology for mathematical simulation; we at¬tribute this development to the fact that computer modeling is relatively inexpensive compared to field data collection and analysis. On-site tests provide the best means of quan¬tifying hydraulic conductivity parallel to bedding and the storage characteristics of the unit. Pump tests with multiple observation wells provide the best information from on site tests. Hydrogeologie boundaries can be located from such multiple well tests. Multiport piezometers provide a means for determining the vertical potential in a single borehole. Borehole geophysics can facilitate the def¬inition of hydrostratigraphic units. Vertical hy¬draulic conductivity is difficult but not impossible to quantify with existing field test methods; labo¬ratory tests of cores fail to give a value represent¬ative of the field situation. The storage characteristics of a confined (artesian) hydro¬stratigraphic unit can be difficult to quantify when pumping changes the confined unit to an uncon¬fined (water table) case after depressurization and dewatering. Transmissivity and storage coefficient can be approximated to some extent for given field con¬ditions by computer modeling if enough is known about hydrogeologic boundaries. Modeling can be used in a trial-and-error approach to match transmissivity and storage coefficients to existing water level data corresponding to estimated discharge rates. A solution can also be obtained using a tech¬nique referred to as the inverse method. Unfortu¬nately, such a solution is seldom unique. Fracture flow models exist but practicality usu¬ally necessitates reversion to a basic Darcy flow model. Data requirements for fracture flow models could be difficult to fulfill where fracture aperture, spacing, orientation, and length are required. Ob¬taining such data at depth prior to mining would be impossible for any mine simulation in fractured media. We are of the opinion that most fractured media simulations can be accomplished using con¬ventional Darcy flow models by viewing the field problem on a macroscopic scale. The real challenge is to delineate hydrostratigraphic units properly in the field. The question of whether a broken-up fault zone is an aquifer or a barrier boundary is seldom simple. The fractures usually can be treated as an equivalent porous medium in either case. Only a few techniques exist for predicting un¬derground mine water inflow. These techniques fre¬quently are designed to evaluate shaft or tunnel inflow under steady-state head conditions in a sin¬gle layer rather than in multiple hydrostratigraphic units. Few computer programs exist that have the

Jan 1, 1986

By M. J. McPherson, R. Venkataramani

R. Venkataramani (Assistant Professor of Mining Engineering, Dept. of Mining, The Pennsylvania State University, University Park, Pa.)-Y. J. Wang and L. W. Saperstein are to be congratulated for their paper on the computer solution of ventilation problems. The limitations on the problem size to be solved by the program (Appendix II) has been outlined in the paper. I would like to add the following additional limitations of this computer program: The dimensions of the variable J1and J2 should be changed to J, (550) and J2 (550) to handle problems containing more than 400 branches, and up to 550 branches. If there are a large number of branches common to the various meshes, another limitation on the problem size will be the dimension of the variable NA. While a higher-order polynomial fitting for the fan characteristic data points is more rigorous, a quadratic relation, if linear interpolation between the points is inadequate, will result in saving computing time without much loss of accuracy. Of course, this can be handled by minor modifications to the existing polynomial fitting routine in the program. M. J. McPherson (Dept. of Mining Engineering, University of Nottingham, Nottingham, England)-The

Jan 1, 1972

By H. Schwartzbart, J. R. Low

Annealed, .Poly crystalline, low carbon steel exhibits a phenomenon known as the "yield point." If such a steel is loaded in tension, the load increases steadily with elastic strain, drops suddenly, fluctuates about some constant load value for a time and then rises with further strain. The load at which the sudden drop occurs is called the "upper yield point"; the load at which deformation proceeds at constant load is known as the "lower yield point"; the amount of elongation at constant load is termed the "yield point elongation." Deformation which occurs during the yield point elongation is heterogeneous in nature, deformed metal existing next to undeformed metal. The drop in load from the upper yield point is concurrent with the formation of a band of deformed metal which usually appears at a stress concentration such as a fillet and at an angle of approximately 45" with the direction of pull. As deformation proceeds during the yield point elongation, the deformed region grows until the entire specimen has been strained an amount equal to the strain in the first band. A phenomenon very often associated with the yield point is that of strain aging. Aging in steels may be of two types: quench aging, or precipitation hardening, and strain-aging. Strain aging differs from precipitation hardening in that if the metal is merely strained instead of given a solution anneal and quenched, it then undergoes changes in properties similar to those observed in quench aging. The yield point effect and strain aging are most markedly exhibited by low carbon steel, but have been observed in other alloys. Numerous explanations for the mechanisms of both phenomena have been advanced, but the evidence for the acceptance of any of the hypotheses is incomplete. One of the explanations of the yield point phenomenon frequently proposed is that there exists a honeycomb of grain boundary material that supports the load above the yield strength of the ferrite and that when this network ruptures, the ferrite flows with no increase in load. This notion was first advanced by Dalbyl in 1913 and has been since put forward in more concrete form by many investigators. The testing of this hypothesis was, in part, the object of the present investigation. Similarly, the mechanism by which strain aging occurs remains to be explained. Presumably, it is a precipitation hardening phenomenon similar to quench aging, the precipitation being initiated by strain. However, it is not known whether the process is a solution and precipitation effect or a change in solubility due to strain. One obvious method of determining whether or not the yield point is a grain boundary phenomenon is to determine if single crystals exhibit a yield point. Low and Gensamer2 have shown that carbon and nitrogen are responsible for the yield point and aging in steel and that these effects can be eliminated by the removal of these elements through wet hydrogen purification. Single crystals that have been grown in wet hydrogen treated material must then be recarburized or re-nitrided in order to evaluate the effect of grain boundaries. In the present investigation, single crystals of iron which had been annealed in wet hydrogen to remove the carbon and nitrogen were cut into two specimens having the same orientation with respect to the tension axis. Of these, one specimen was pulled in tension in the wet hydrogen treated state and the other was carburized or nitrided and tested similarly. All the crystals were examined for a yield-point and strain aging. The grain boundary hypothesis for the explanation of the yield point in steel has been tested only indirectly previously. Arrowsmith,3 Andrew and Lee,4 Edwards and Pfeil,5 Fell,6 Ludwik and Scheu,7 Winlock and Leiter8 and others found a decrease in proportional limit and yield point effect with an in-

Jan 1, 1950

By H. A. Doerner

Tellurium is a silver white solid with metallic luster, the e17atal.line torm being ver., brittle aud e.g,s!ly powdered. It has a specific gravity of 6,27, melta at 45a0c. and boils at red het, giving off a. golden 1ellow vapor when air 11 excludei. When heated in air, telluri'UiD burns with a bl\te name tinged with green, and evolves wh1 te vapors ot tellurium dioxide. An amorphous form of tel­lurium, obtained by red.uction and precipi ta.tion from so).ution, haa II specific gr1.vity ot 6,015, and when heated ia cho.nged to the cry:.,talline variety. Telluri,a 11 insoluble in water, c&rbon diaiJ.phido, or h;rd.rochl oric acids, but it 11 41a-1olved bJ nitric or concen t1·ated. sulphi.U·ic acid. It 1..oea not tamiah in moiet ah•• 11 ree11tant to alkaline solutions, e,;:ctpt concentrated KOB, but it 11 cliaaolvecl by tuaed. &lkl 1••. I ts 11.to!!lic weight h..'l.a been the "J.Ubject ot mch controverq, bu\ t.he value 137 .5 :.a bl!ten generally accepted, Tho chflmietr:, of tellurium ia eim1lar to that ot IUlphur. It tonne throo xid.ee TeO, To02, and Te0 , al10 tellur14ea, t•llurite,, and. tellur1.t11, A number of halide compoWld.1, a 3iulph1de, and. a .ulpbat.e are known.

Aug 1, 1922

By W. D. Robertson, E. G. Grenier, V. F. Nole

The electrical, mechanical, and corrosion cracking properties of an age-hardenable Cu-Ni-Si alloy have been studied over a range of time, temperature, and deformation states for the purpose of determining the relationship between the properties and the structural state. The precifitate has been identi3ed as and the sites of preferred precipitation have been located by electron microscope studies of the structures developed by various combinations of heat treatment and plastic deformation. An extreme form of deformation banding has been observed in the aged alloy that results in high strain concentration in bands lying parallel to {111} planes. These bands are the structural paths along which transcrys-talline cracks propagate in the deformed alloy. The observations provide a basis for a general mechanism of transgranu-lar corrosion cracking of face-centered cubic alloys in terms of stacking fault probability. AMONG the age-hardening copper alloys the copper-nickel-silicon (Silnic Bronze) type is outstanding in exhibiting a high strength combined with a considerable capacity for cold working, a relatively high conductivity, and a low to negligible susceptibility to stress corrosion cracking. It is not a new alloy and it has been the subject of a number of investigations,1-5 which were made primarily to establish practical composition and heat treatment limits. The structural characteristics of the aging processes in this alloy have not previously been studied in detail. This particular investigation was undertaken to explore, in detail, and over a wide range of conditions, the properties obtainable by various combinations of working and heat treatment and to correlate structural changes with the observed mechanical, electrical and corrosion properties. MATERIAL AND PROCESSING Eight different commercial heats of the alloy were made and used in the investigation. The range of composition among the eight heats is shown in Table I. Billets, 8 by 24 in., were cast into water-cooled molds, extruded to 1.687-in. rod, and quenched in water after extrusion. Extruded material was rod rolled to 0.750 in., annealed at 1450° F for 2.5 hr, and quenched in water. Subsequent working operations were performed by tandem rolling to various sizes depending on the degree of reduction required. Final cold-working operations were performed by drawing to a uniform size of 0.187 in. diam and straightening by a roller straightening machine (Lewis). The combinations of heat treatment, working and aging that were investigated are summarized in Table 11; the various treatments were performed in the order given in each row of the table, and they will be subsequently identified by the symbols shown in the first column. SOLUTION TREATMENT All material investigated in the cold-worked condition, or cold worked prior to aging, was solution

Jan 1, 1962

By Bo-Hyun Kim, Mark K. Larson

"Researchers at the National Institute for Occupational Safety and Health (NIOSH) have advocated the use of instrumentation in underground mine ground control studies to aid in understanding failure mechanisms and to calibrate numerical models. The purpose of these efforts is to reduce accidents and fatalities in underground mines resulting from inadequate design of mining layout or supports. A recent examination of some results of stress change measurement raised some questions about the validity of elastic solutions in ground, such as coal. Particularly under deep cover as is prevalent in the western United States, the coal around a borehole would likely have yielded so that post-yield behavior would govern the response of the instrument.A numerical experiment was conducted by NIOSH researchers using the FLAC software (Itasca Consulting Group, 2016) to investigate the response of the borehole pressure cell (BPC) and the biaxial stressmeter to varying degrees of plastic behavior. The pre-encapsulated BPC cell pressure exhibits increasing departure from the elastic case with decreasing post-peak-strength slope of the stress-strain curve. On the other hand, because the BSM usually provides much more confinement to the surrounding rock than does the BPC, the measurements obtained from the BSM do not depart significantly from the changes in secondary principal stresses and directions as calculated by the elastic solution.INTRODUCTIONSeveral years ago, Larson et al. (2000) described several instruments that NIOSH had used in underground field studies and how to monitor them with dataloggers. This information is still relevant because of the need to understand how excavation affects the stability of mines and thus, the safety of mining personnel. One class of instruments described in that paper includes those instruments that measure change in rock stress. Although several such instruments might be used to measure stress change, the focus of this paper is on two instruments with which NIOSH has had more recent experience—the borehole pressure cell (BPC) (Geokon, 2018a; RST Instruments, 2018) and the biaxial stressmeter (BSM) (Geokon, 2018b). Other instruments, such as the CSIRO hollow inclusion stress cell (HICell) (Earth Sciences, 2019; Worotnicki and Walton, 1976) may be included in future studies.Early studies in the development of the BPC were those of Panek and Stock (USBM, 1964), Sellers (1970), Lu (1984), and Babcock (1986). Babcock’s work is particularly useful, but his setting and testing range was far below what we experienced in the NIOSH study, and it was Babcock’s data reduction scheme from his laboratory experiments that was used to calculate stress change in the NIOSH study (NIOSH, 2019a)."

Jan 1, 2019