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This paper refers to the open cut mining practice developed at Western Mining Corporation's Kalgoorlie Gold Operations (K.G.O.). Mining activity was centred attwo areas, namely W.M.C.'s Siberia "Sand King" and"Missouri" open cuts plus W.M.C.'s "Great Boulder" and K.M.A.'s "Horshoe" and "Morrison -Hannan's Star" open cuts in Fimiston.Kalgoorlie Gold Operations was set up initially to look after W.M.C.'s open cut interests in and about the Kalgoorlie area. The first mine commenced was, the Sand King open cut, approx 75 km NW of Kalgoorlie. it was here that the requirement for a highly selective form of mining first became apparent.

Jan 1, 1984

By H. Rees

This paper supplements and brings up to date a report prepared earlier this year and presented at the Eleventh Pan American Railway Congress in Mexico City. Most of the original report is contained in this paper in order to acquaint the reader with the project background. On December 1, 1961, construction of this locomotive was completed. Stationary testing started immediately, and a host of problems in various areas were uncovered. Many of these had no relation to the use of coal in a direct fired gas turbine. All of them emphasized the problems which plagued previous projects of this kind. In 1944 the Locomotive Development Committee of Bituminous Coal Research, Inc., was formed to study the problems of combustion, coal handling, and fly ash removal which would have to be solved before coal could be used to fire a gas turbine. By 1947 this committee was composed of the chief executive officers of nine eastern railroads and five eastern coal companies. All of the members of this committee were vitally concerned in a coal fired gas turbine because coal cost only one-fourth as much per heat unit as fuel oil. A number of research projects were started to develop and test components on a small scale. This included work at John Hopkins University, Battelle Memorial Institute, Institute of Gas Technology at Chicago, Purdue University, and Southern Research Institute. By 1946 a pilot plant had been installed at the Dunkirk, New York plant of Alco Products Div. of American Locomotive Co. The U. S. Bureau of Mines made available to the Locomotive Development Committee (hereafter called LDC) a Houdry process gas turbine plant, originally destined for a Russian oil refinery. The full scale pilot plant was used to evaluate the results obtained from the small scale studies under actual gas turbine conditions. Operation of this plant disclosed a number of problems which had not been discovered in the small scale tests. By 1951 four 250 hr tests had been conducted with the Houdry gas turbine to test out a variety of equipment. The major problem concerned the removal of abrasive fly ash from the products of combustion so that wear on turbine blades would not be excessive. The first 250 hr test showed that the original fly ash separating equipment was inadequate. Large ash particles passing through the turbine blading were nicking the leading edges of the first row blades. At the conclusion of the second 250 hr test, erosion was so severe that the first row of stator and the first row of rotor blades were replaced. At the end of the third 250 hr test, it was necessary to replace the first three rows of stator blading. The fourth test was used to test out a new design fly ash separator developed by LDC and named the Dunlab tube. This device gave more encouraging results than any of the others tested. Early enthusiasm for overcoming major difficulties had resulted in placing an order in 1946 with Allis-Chalmers Mfg. Co. for a 3750 hp regenerative gas turbine. The gas turbine, together with associated combustion and ash removal equipment, coal handling equipment, generators and gear reduction unit was installed at Dunkirk by 1951. A 750 hr test was made in 1952 with the LDC-Allis Chalmers gas turbine power plant. At the end of this test it was necessary to replace the first four rows of both rotor and stator blading. Rows 5 and 6 did not require replacement. In 1953 the American Locomotive Co. joined with LDC and assumed an active role in equipment development and manufacture. During 1954 LDC-Alco operated the rebladed gas turbine 300 hr to determine if a new fly ash separator was adequate. Performance of the improved separator was considerably better, but trouble was experienced with clogged blowdown lines from the Dunlab tubes. When these lines clogged it permitted the passage of abrasive particles. In 1955 a total of 1421 hr was run. This included 243 hr of cycle operation on Union Pacific coal from the D. O. Clark mine at Superior, Wyoming. During the 243 hr a total of 370 tons of coal was consumed. The purpose of this test was to determine if U.P. coal was suitable for use in a coal fired turbine. It was the unofficial opinion that it was as good or better than the eastern coals that had been tested.

Jan 1, 1964

By T. M. Barczak

Stoppings are required to resist lateral forces on the face of the structure to control pressure differentials created by ventilating air. The design criteria in other parts of the world, including Australia, exceed this requirement by specifying over pressurization control to as much as 14 kPa (2 psi) in the active sections and 35 kPa (5 psi) in the main ventilating control areas. This is done to provide protection to the mine workers from explosive or air blast events within the mine that can create this over pressurization. The National Institute for Occupational Safety and Health (NIOSH) has been conducting research to develop a new testing protocol for rating mine ventilation stoppings. The premise of this work is that arch-loading conditions more accurately reflects the transverse load capabilities of stoppings in underground coal mines than the freestanding flexural strength test specified in the current Code of Federal Regulations (CFR). This work clearly shows that the transverse load capabilities of dry-stacked, mine ventilation stoppings are dependent upon the material strength of the block and the height and thickness of the wall, none of which are part of the current CFR criteria based on ASTM E-72 specifications. This paper compares the transverse load capabilities of several block materials and wall dimensions commonly used in stopping constructions based upon simulated three-hinge, rigid-arch loading tests of half-wall constructions in the NIOSH Mine Roof Simulator. The results indicate a wide-range of transverse load capacities, ranging from as low as 21 kPa (0.3 psi) to as much as 117 kPa (17 psi) for the conditions evaluated in this study. The current CFR criteria do not distinguish between applications of these stopping designs despite their wide variance in transverse load capabilities, which is not conducive to employing ventilation control strategies that isolate certain sections of the mine to prevent injury to mine workers.

Jan 1, 2009

By F. F. von Glehn

There is no doubt that simulated ventilation networks must be adequately verified before they can be extrapolated and used for predictive purposes. There are two general approaches as to how the verification can be established and these are summarised as follows; The first approach is to measure all individual branches with trailing hoses or barometers to get individual pressure drop and flow per branch and then calculate individual resistance factors for input into the software. The simulator is run, checking that the output makes general sense (check some sensitivities if possible). The network is now considered as verified. The pressure drop to be measured is relatively small and thus it is inherent that the measured set of individual K factors will be imprecise no matter how much care is taken in the measurements and the resultant simulations will inherit the same problem. In the second approach, the network is assembled using estimated (Atkinson) K factors (based on physical features of airway, past experience and catalogued typical K factors). Only the main primary flow rates are measured and hence the relative distribution of the primary ventilation in the main airways is determined (probably about 10 off primary air flow measurements). Main critical pressure differentials at main and booster fans and across critical doors are measured (probably about 6 off primary pressure differential measurements need to be made). The simulator is run and the computer model is used to iterate and select an updated suite of K factors so that the flow balances and pressure differentials are correctly simulated (typically only 2 or 3 iterations are all that is needed). The network is now considered as verified. The pressure differences to be measured will be substantial in absolute terms and can be measured with high precision. Also, because only primary flows are measured, these will generally be measured at higher air speed points and hence improved relative accuracy. This leads to more accurate simulation results. This paper examines the advantages and disadvantages of the two approaches. 1 Background

Jan 1, 2009

By B Darlington, L Sandberg, O Vallati

The D47 and D39 Mechanical Dynamic Extra bolts (D47 MDX and D39 MDX) have been developed in response to the ever-increasing demand from the mining industry for rock bolts with high dynamic capacity. To prove such capacity, Sandvik has performed numerous in situ dynamic testing with the unique Dynamic Test Rig (DTR) (Darlington, Rataj and Roach, 2019; Roach, Rataj and Darlington, 2019). To complement the collection of testing data, Sandvik, in collaboration with the Swedish Research Institute for Mining, Metallurgy and Materials (Swerim) have performed additional experiments in laboratory condition using Swerim’s new drop test rig. This rig utilises a momentum transfer method to apply a dynamic load to the bolt. The sample falls together with the mass until the support beam impacts stationary dampers and the momentum energy is transferred to the bolt. Part of the charged energy is released by the dumpers while the remaining portion is absorbed by plastic deformation and/or displacement of the ground support element. The D47 and D39 MDX bolts have been tested at Swerim’s test facility with different levels of input energy. Six tests were performed at the specification energy of 36 kJ and six tests were carried out with the maximum allowable energy from the facility, ie 44 kJ. The bolts confirmed their dynamic performance absorbing the input energy without failure. The D47 MDX bolt absorbed up to 33 kJ with 150 mm displacement while the D39 MDX bolt absorbed up to 35 kJ with 162 mm displacement. This work will present an overview of the drop test rig at Swerim’s facility and a collection of results of the test performed on the D47 and D39 MDX bolts. The test method and results will be analysed and compared to the tests carried out with the in situ DTR.

Nov 29, 2022

By Seth C. Schaefer

The Federal Bureau of Mines studied the Gibbs free energies of formation of chromous fluoride (CrF2), chromic fluoride (CrF3), and chromium (II,III) fluorides (CrF2.40 and CrF2.45) with high-temperature galvanic cells employing calcium fluoride doped with 1 mole-pct yttrium fluoride as the electrolyte. Free-energy changes were obtained from open-circuit potential measurements for the following cells: Cr, CrF2 // CaF2 // NiF2, Ni (a) NiO, NiF2 // CaF2 // CrF3 , Cr203 (b) CrF2 , CrF2.40 // CaF2 // NiF2, Ni (c) and CrF2 ?45 , CrF3 // CaF2 // NiF2, Ni (d) with the following overall reactions Cr(s) + NiF2 (s) = Ni(s) + CrF2 (s) (1) 3NiO(s) + 2CrF3 (s) = 3NiF2 (s) + Cr203 (s) (2) 5CrF2 (s) + NiF2 (s) = 5CrF2.4O (s) + Ni(s) (3) and 3.64CrF2.45 + NiF2 (s) = 3.64CrF3 (s) + Ni (s) . (4) These results were combined with the best available literature values of ?Gf° of NiF2, NiO, and Cr203 to deduce Gibbs free energies of formation for the chromium fluorides expressed as follows: ?Gf°(CrF2) = -179.31 + 24.33 X 10-3T ± 0.43 kcal-mole. (5) (858.1 - 964.9 K) ?Gf° (CrF3) _ -226.16 + 1.82 X 10-3T ± 0.79 kcal/mole (6) (880.8 - 957.8 K) ?Gf°(CrF2.40) _ -213.65 + 32.14 X 10-3T ± 0.44 kcal/mole (7) (0053.9 - 936.8 K) and ?Gf°(CrF2.45) _ -176.17 - 12.67 X 10-3T ± 0.80 kcal/mole (8) (875.1 - 937.6 K). Free energies and equilibrium fluorine pressures for three univariant and one bivariant equilibria are illustrated.

Jan 1, 1976

By Nawshad Haque, Leanne Smith, Hal Aral, Joseph Cho, Warren Bruckard

"Water availability is one of the principal parameters in determining the feasibility of mining projects in arid and semi-arid regions. The volumetric water footprint (VWF) of a conceptual model of a copper flotation plant was found to be 2.45 kL/t Cu ore, compared with an actual measurement reported in the literature of 2.72 kL/t Cu ore. The flowsheet considered included mineral processing stages such as crushing, screening, grinding, classification, separation, flotation, thickening and filtration. The effect of a number of variables on the VWF was evaluated, including solid/liquid ratio, feed mass flowrate, ore loss, water loss, moisture content of ore, ore grade and water recycling. The use of seawater with recycling provided the most environmental and economic advantage among several scenarios evaluated. The study assumed a price of $1/kL freshwater, $4/kL for transport over a 200 km distance at 2,000 m altitude and $4/kL for water treatment. The water related cost of the desalinated seawater use scenario was A$493/t Cu concentrate, while the water related costs of fresh water and blended water scenarios were A$308/t and A$268/t Cu concentrate, respectively. The water related cost (fresh water scenario) accounted for 44% to 49% of the entire mining and processing costs that included drilling, blasting, loading, hauling, crushing, grinding and concentrating. The total overall cost was A$435/t Cu concentrate for the seawater with recycling, compared to A$451/t Cu concentrate for the fresh water with recycling case.INTRODUCTIONReducing the water footprint (WFP) by utilising alternative water sources has been a focus of mining projects due to increasing concerns about water scarcity and growing energy costs. The global mining industry can expect to experience fresh water shortages in the future, and saline or hyper-saline water may be the only available water source to process minerals in arid regions. Extensive studies on alternative water sources (e.g. seawater, desalinated seawater, blended water) and the reuse of process water have recently been conducted (Moreno, Aral, Cuevas, Monardes, Adaro, Norgate & Bruckard, 2011; Aral, Mead, Cuevas, Davey & Bruckard, 2010). Such studies provide sustainable and economic strategies for mines and concentrators in the arid or semi-arid regions of the world such as in Chile, Peru, Indonesia, and Portugal. More work, however, is needed to confirm water consumption data for different base metal flowsheets and use this data to develop water models that can lead to reduced WFPs and more sustainable water usage in the mining industry."

Jan 1, 2016

The properties required for a com-pound to form useful thermoelectric materials are described. Uranium compounds which might have these properties are reviewed. Several of these compounds have been prepared and fabricated into compacts. The apparatus used for hot pressing, and for the measurement of thermoelectric power, electrical conductivity and thermal conductivity, is described. Detailed attention has been given to the properties of the nitrides. Preliminary studies on a number of other uranium compounds are reported. The figures of merit of the best materials so far examined are one-tenth of those necessary for a useful thermo-electric material. THE efficiency of thermoelectric materials for power generation and cooling is determined by their figure of merit, Z = a2 a/K, where a, a and K are thermoelectric power, electrical conductivity and thermal conductivity, respectively. It is well known that the largest values of Z are achieved with semiconductors (1). High mobility of charge carriers is necessary for simultaneously high thermoelectric power and electrical conductivity.The properties required for a com-pound to form useful thermoelectric materials are described. Uranium compounds which might have these properties are reviewed. Several of these compounds have been prepared and fabricated into compacts. The apparatus used for hot pressing, and for the measurement of thermoelectric power, electrical conductivity and thermal conductivity, is described. Detailed attention has been given to the properties of the nitrides. Preliminary studies on a number of other uranium compounds are reported. The figures of merit of the best materials so far examined are one-tenth of those necessary for a useful thermo-electric material. THE efficiency of thermoelectric materials for power generation and cooling is determined by their figure of merit, Z = a2 a/K, where a, a and K are thermoelectric power, electrical conductivity and thermal conductivity, respectively. It is well known that the largest values of Z are achieved with semiconductors (1). High mobility of charge carriers is necessary for simultaneously high thermoelectric power and electrical conductivity.

Jan 1, 1963

Abraham E.M., 465 Adam K., 151, 203, 249 Agioutantis Z., 137, 389 Alley M.M., 301

Jan 1, 2007

By B. Nemutudi, X. Zhang, B. McFadzean, P. E. Ngoepe, P. P. Mkhonto, S. Pikinini

The comparison study on adsorption of potassium normal butyl xanthate (PNBX) and sodium (nbutyl) dithiocarbamate (SNBDTC) on sperrylite mineral forms a basis in understanding the floatability improvement and paves a way for the design of collectors that may impact on a wide range of arsenide minerals. This study used a computational density functional theory (DFT) and experimental microcalorimetry approach to determine the adsorption energies of PNBX and SNBDTC collectors onto a sperrylite mineral surface. From a computational aspect, we considered the most stable surface plane of (100) surface, which had been found to give the lowest surface energy, compared to the other surface planes. It was observed that the PNBX and SNBDTC preferred to bridge on the As and Pt atoms through the S atoms. These findings showed that the collector adsorbed on the surface through both Pt and As atoms and indicated that the As atoms were significantly active in the adsorptions. We found that the adsorption energies were in the order: SNBDTC (–278.38 kJ/mol) > PNBX (–270.92 kJ/mol), indicating that the dithiocarbamate had stronger exothermic adsorption than the xanthate. From the microcalorimetry test it was also found that the SNBDTC was more exothermic than the PNBX and the adsorption energies were: SNBDTC (–473.50 kJ/mol) > PNBX (–331.13 kJ/mol). These results showed that the nitrogen atom in the SNBDTC collector had a great influence on the adsorption strength of the collector on the mineral surface. This is due to the electron deposition behaviour of nitrogen atoms compared to the electron withdrawing character of oxygen and as such the SNBDTC showed better collecting ability than the PNBX. These results paved the way for the design of collectors for sperrylite and other arsenide minerals and suggested that nitrogen in a collector may significantly improve the ability of the collector for improved recovery. Keywords: Computational modelling, microcalorimetry, SNBDTC and PNBX collectors, adsorption energies

Jan 1, 2020

By SMF Hossaini

With the aim of a clearer understanding of the applicability of existing empirical equations for blast induced ground vibration, an investigation has been conducted on three mostly applied forms of such equations. The effect of explosive type on the applicability of these equations has been assessed by analysing 44 sets of data produced by using two types of explosives, namely ANFO and slurry explosive, in an open pit coal mine. The analysis of the data has revealed that the type of explosive affects the applicability of the criteria of the three equations. All three criteria have better correlation with the data of shots in which ANFO was used than the shots with slurry explosive. However, the applicability of one of the criteria is reduced, by far, only by replacing ANFO with slurry explosive for the same ground conditions. It was also found that one of the parameters of these criteria (i.e. “k”) is significantly sensitive to the type of explosive in all the three equations. The degree of influence to the values of “k” obtained by the variation of explosive from ANFO to slurry explosive in the three equations is 76.3%, 811% and 39%. This implies that “k” is not only dependant on ground conditions, as stated in most previous publications, but is also strongly a function of the type of explosive.

Jan 1, 2004

By K. O. Bennington

The thermodynamic properties of two manganese silicates, pyroxmangite and fowlerite (zincian rhodonite), were experimentally determined by the Bureau of Mines. The standard enthalpies of formation were determined by hydrofluoric acid (HF) solution calorimetry, the low-temperature heat capacities by adiabatic calorimetry, and the high-temperature heat capacities by differential scanning calorimetry over the range 322 to 1,372 K. Data for the standard enthalpy of formation (AH298), the derived standard entropy (S298), and the standard Gibbs energy of formation (AGf 298) are as follows: Pyroxmangite [(Mn0.9554Cao,0446)(Si03)J- AHf298 319.668±0.46 kcal/mol AH298 (from oxides)... -7.215±0.11 kcal/mol 5295 23.785±0.048 cal/(mol'K) AGf298 -301.190±7.96 kcal/mol Fowlerite [(Mno.7o3Zno.0884Ca0.2086)(Sio3)]--AHf298 ?... -329.914±0.419 kcal/mol AH298 (from oxides)... -8.400±0.104 kcal/mol 5598 21.949±0.059 cal/(mol-K) AGf298 -310.716±7.99 kcal/mol These experimentally determined values were combined with data from the literature to calculate the Gibbs energies and equilibrium constants of formation over the temperature range of the measurements. Standard enthalpies, Gibbs energies, and equilibrium constants of formation are given as a function of temperature from both the elements and the constituent oxides.

Jan 1, 1987

By C. F. Lucks, W. D. Wood, H. W. Deem

Electrical ad thermal-conductivity measurements have been made on titanium and 6 titanium alloys. The following expression was derived for calculating thermal conductivity from electrical conductivity: K = 0.626 s T x 10-8 + 0.00497 where K = thermal conductivity, cal sec-1 cm-2 cm0C-1 s = electrical conductivity, ohm-]cm-1 T = temperature, deg Kelvin This expression gives calculated thermal conductivities that are not in error by more than 10 pct from the experimental values for A-55 titanium and the 6 alloys measured; namely, A-110AT, C-110M, C-130AM, Ti-6A1-4V, Ti-140A, and Ti-155A, which are representative of the presently available commercial a and a-ß titanium alloys. THERMAL conduction in a gas, liquid, or amorphous solid is accomplished by energy diffusion from molecule to molecule, a relatively slow process. For this reason, such materials have a low thermal conductivity. When a material is crystalline, there is in addition a heat transfer by a vibratory motion of the crystal lattice. It is the contribution of this lattice conduction that makes a crystal a much better conductor than a gas, liquid, or amorphous solid. Lattice conduction, however, does not account for the relatively enormous thermal conductivity of a metal. This is explained by the freedom of movement of valence electrons. These valence electrons drift in a metal in a direction toward a drop in electrical potential and, to a lesser degree, in the direction of a temperature drop in the metal. Since both the electrical and thermal conductivities of a metal depend upon the presence of free electrons, there should be some relatively simple relation between the two. Wiedemann and Franz in 1653 first discovered an approximate empirical relation between the electrical and thermal conductivities of metals at the same temperature. This ratio varies appreciably with temperature, and Lorenz later showed that by adding a temperature factor to the Wiedemann-Franz ratio the value of K/(s T) is constant, where K is the thermal conductivity, a the electrical conductivity, and T the absolute temperature. This Lorenz constant shows a greater variation for alloys than it does for pure metals, the ratio increasing slightly as the proportion of alloying elements increases. It has been found that a closer correlation between electrical conductivity and thermal conductivity can be obtained by means of an equation of the form K - A s T + B [1] where A and B are constants. In this equation the term AsT is the contribution of electronic conduction and B is the contribution of lattice conduction to the total thermal conductivity. EXPERIMENTAL MEASUREMENTS Electrical-resistivity and thermal-conductivity measurements on titanium and 6 titanium alloys serve as the basis for determining an equation of the K = AsT + B type for titanium alloys. Specimens—Table I shows nominal compositions of the 7 metals on which electrical and thermal conductivities were measured. The electrical and thermal-conductivity specimens for each alloy were taken from stock of the same heat and usually from adjacent sections of the same bar. All of the metals measured were in a mill-annealed condition. Methods—Electrical-resistivity measurements

Jan 1, 1959

By M. Hancer, J. D. Miller

It is known from soluble salt flotation practice that the K, Mg double salts of kainite (KClMgSO43H2O), and carnallite (KClMgCl26H2O) are difficult to float and must be converted to other salts such as schoenite (K2SO4MgSO46H2O) and sylvite (KCl) in order to recover potash values. The flotation characteristics of these double salts have now been confirmed in some detail by carefully controlled laboratory experiments with both cationic and anionic collectors. The experimental results are discussed in view of recent experimental findings regarding the flotation characteristics of simple salts, in which the flotation response was shown to be determined by the interfacial water structure and whether the salt could be considered to be a water structure maker or a water structure breaker. The same approach can be use to explain the flotation response of the potassium double salts ; schoenite, kainite, and carnallite. In addition, the sign of the surface charge of schoenite (K2SO4MgSO46H2O), was determined as a function of pH from nonequilibrium electrophoretic mobility measurements. Schoenite appears to exhibit three charge reversals (CR) which can be explained based on surface hydrolysis reactions. The flotation behavior of schoenite is further considered based on solution chemistry calculations, electrophoretic mobility measurements, and microflotation results.

Jan 1, 2001

By Robert M. Doerr

The purpose of the investigation was to determine the oxidation behavior of selected tungsten-cobalt alloys. Specimens of Wand W-Co containing 0.7, 1.7, 3.4, and 9.7 weight-percent Co were subjected to pure 02 at 1,000° and 1,100° K, and specimens of W-Co containing 29.8 weight-percent Co, at 1,100° K. Reaction kinetics were determined volumetrically. For specimens other than those containing 29.8 percent Co, the reactions proceeded at about a constant rate at either temperature, indicating the formation of a scale of constant protectivity; the reaction rates were essentially independent of the Co concentration. The scales on these alloy specimens consisted principally of WO3 and CoWO4. Specimens of a 29.8 weight-percent Co alloy, consisting primarily of the W6CO7 phase, oxidized with only slight deviations from the parabolic rate law at 1,100° K. The protective scale on these specimens consisted chiefly of Co3O4, CoW04, and W1 8°49; Co3O4 was outermost, and the W18O49 was adjacent to the alloy. The results suggest that the Co-rich outer scale inhibited the inward transport of 0 to an extent sufficient to greatly limit the amount of the nonprotective WO3 formed, so that protective W18O49 formed instead.

Jan 1, 1967

By D. A. Stanley

The Bureau of Mines is investigating a method of dewatering flocculated fine-particle waste that involves treating the waste with a high molecular-weight polymer such as polyethylene oxide (PED) followed by dewatering on a static screen and/or in a trommel. Dilution of the polymer solution used for dewatering and use of the ion-exchanged form of the montmorillonite clay were found to be major factors determining the amount of polymer required to dewater clay-containing slurries. The amount of polymer, A, required to dewater ion-exchanged montmorillonite can be described by the equation, An = kC + b where n, k, and b are empirical constants and C is the concentration of the polymer solution used for dewatering. Clays that require large amounts of polymer for dewatering also dewater to a lower solids content. The concentration of the polymer solution is important because it affects the radius of the polymer coil in solution and hence its ease of transfer to a bridging configuration by shear. The constant, n, a function of the charge to hydrated radius of the exchange ion, relates to the strength of the bond between the polymer and the surface of the clay through a water bridge. The constant k is related to the hydrated radi-us for sodium or to the unhydrated radius for the other exchange ions.

Jan 1, 1986

By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.' More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.' This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.' These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer's6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965

By R. D. Pehlke, J. V. Gluck

The limiting activity coefficient of zinc in a "binary " solvent has been described for several dilute ternary solutions by combining literature data from recent interaction studies in the terminal regions with thermodynamic data for the central regions. Results are discussed in terms of the Alcock and Richardson random solution model. The observed behavior agrees semiquantitatively with predictions using the model. RECENT efforts in the thermodynamics of dilute ternary liquid metallic solutions have been mainly concerned with the interactions between two dilute solutes, that is, the terminal region at an apex of the composition diagram.'-' A more general case is that of the behavior of a dilute solute over the full range of a ternary system, or, more specifically, the limiting activity of solute i as projected to the k-j binary side of the i-j-k composition triangle. An implication of this is that the interaction between i and j at the k apex should connect in some way to the interaction between i and k at the j apex. A model to characterize various types of expected behavior has been discussed by Alcock and Richardson.9,10 Such behavior can range from a simple linear relation for In yi over the 1-k binary to more complex curved relations which depend on various assumptions regarding the heat of solution in the j-k binary system and the presence or absence of clustering with solute i. Quantitative data to assess these concepts have been limited primarily to the cases of nonmetallic interstitial solutes in ferrous solutions. Alcock, Richardson, and various coworkers9-13 have discussed the behavior of oxygen, sulfur, silicon, or hydrogen in dilute solution over the range of iron + metal systems; however, the only data considered by them for substitutional nonferrous metallic solutions were the results of Elliott and Chipman concerning the activity of cadmium in the Pb + Sn, Pb + Bi, and Pb + Sb systems.9 These data were limited and did not cover the terminal regions in detail. An opportunity to extend the Alcock and Richardson considerations to the dilute solution of zinc in various "binary" solvents has been afforded by combining results of several of the recent investigations of ter-minal-region interactions with previous data from the literature for the same more concentrated solutions. RESULTS AND DISCUSSION The results of the analysis are shown in Figs. 1 to 5 where the log activity coefficient, (In yZn)xzn--o, is plotted vs the composition of the "binary" solvent. In these plots the end points are the values for In yzn in the appropriate binary solution with Bi, Pb, Sn, Cd, or In at the indicated temperature—usually 550°C (823°K). For the terminal regions the slopes were drawn using the first-order interaction parameters taken from various studies reported in the literature. The data points shown in the central regions were obtained by the short extrapolation to infinite dilution of the logarithm of the activity coefficient calculated from thermodynamic studies reported in the literature for the same systems. The sources of the data are indicated on each figure. Second-order effects were not considered. Reasonably smooth curves can be drawn to connect the central region with the terminal regions for the Zn-Pb + Bi system, Fig. 1, the Zn-Pb + Zn system, Fig. 1, and the Zn-Bi + Cd and Zn-Bi + Sn systems, Fig. 2. As shown in Fig. 2, where central region data are available from two independent investigations, the agreement is quite good. The Zn-Pb + Cd system does not appear to be as well behaved as the previous four, Fig. 3; however, this type of behavior has also been

Jan 1, 1970

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By Philip D. Anderson, Ralph Hultgren

Heat contents of extremely pure iron were measured over the range 300"to 1433"K, using a diphenyl ether calorimeter. Results from three samples containing widely differing impurities agreed with one another and with Previously reported results at higher temperatures (1184 ° to 1809°K) by Olette and Ferrier. From these data a table of heat contents of iron has been Prepared which is believed to be more accurate than those previously available. CP values have been derived which are consistent with these heat contents, with the best experimental Cp data, and with the thermodynamic conditions of equilibrium between bcc and fcc iron. The opinion is expressed that low-temperature extrapolations of presently known Cp values for y-Fe are not reliable. It would seem that the thermodynamic properties of iron, which is by far our most important metal, should have been well established long ago. This is not the case, however. As discussed by Olette and Ferrier,' there is objection to every earlier heat content measurement. While the best true Cp determinations agree well at temperatures below the Curie point, there is wide divergence at higher temperatures. Several investigators have examined available data and attempted to calculate thermodynamic functions for iron that are consistent with the two equilibrium temperatures of bcc and fcc iron. The two primary efforts were those of Austin' in 1930 and Darken and smith3 in 1948. The recommended values differ considerably; integration of Austin's Cp values leads to a heat content at 1100°K which is 300 cal per g-atom higher than the value recommended by Darken and Smith. The compilation of Fisher4 in 1949 was based on the selection of Austin. In 1956, Weiss and Tauer obtained yet another set of values by resolving Cp values into components due to dilation, lattice vibration, electronic excitation, and magnetism. The magnitude of contribution by each component and its dependence on temperature was estimated by semiempirical means. Their values are not self-consistent in that they do not form smooth curves when plotted vs temperature; moreover, their calculations cannot easily be repeated since they do not give the values of some of the parameters used. Clearly, experimental values for iron were in a most unsatisfactory state. The presently described measurements of the heat content of iron were therefore undertaken, covering temperatures as high as 1433°K. While the work was in progress, the high-temperature (1193" to 1789"K) heat content measurements of Olette and Ferrier' were published; in the region of temperature overlap the present results agree with Olette and Ferrier well within experimental accuracy. It is believed that the present results, combined with those of Olette and Ferrier, provide for the first time a reliable set of heat contents of iron from room temperature to the melting point. From these data, guided by available Cp measurements, it proved possible to derive Cp, entropy, and free energy function values for @-iron from room temperature to the melting point, and for y- iron in the temperature region of its stability. Exhaustive study led to the conclusion that extrapolations of y-iron functions to room temperature were not reliable enough to be useful; hence these have been omitted from the tables. EXPERIMENTAL Materials. Three samples of extremely high purity iron from different sources, containing widely different impurities, were measured. The first of these, designated "Chipman", was kindly supplied by Dr. K. K. Kelley of the U. S. Bureau of Mines from a lot which was made many years ago by Dr. John Chipman of the Massachusetts Institute of Technology. The second, designated6'Teddington", was supplied by the National Physical Laboratory, Teddington, England, from a lot zone-refined by them. The third sample, designated "Irsid", was supplied by the Institute de Recherches de la

Jan 1, 1962