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By S. Tandon

Equilibria studies of selenium distribution for sodium-borate slags were initiated at 1473k under reducing condition as a function of slag composition and alloy composition. The Se distribution coefficient (% Se in slag/% Se in metal) increased from 0.4 to 2.9 with increase in basicity (0.53 to 0.86) for Cu-0.446% Se alloy. However, the results are not very useful from industrial application viewpoint. Therefore, in order to improve the distribution of Se, CaO (10% to 50%) was added to the sodium-borate slag of basicity 0.864. On addition of 502 CaO, the distribution coefficient increased roughly by 100% for slag composition - 44.5% Borax, 22.2% Na2C03, 33.3% CaO and Cu-0.44677 Se alloy. Further, the value of this distribution coefficient has been found to increase by an additional 80% on addition of 20% CaF2 to the above slag for all Cu-Se alloy compositions. Also with increase in initial concentration of Se, the distribution coefficient has been noted to increase.

Jan 1, 1992

By Paktunc. A. Dogan, Nand K. Davé

Unsegregated pyritic uranium mill tailings from Elliot Lake, Ontario, with and without limestone amendment, were subjected to column leaching experiments for the purposes of predicting the onset of acidic drainage and the magnitude of metal and radionuclide release under various treatment and control strategies. The unamended tailings produced acidic drainage after approximately one and a half year. The tailings mixed with various grain-sized limestone did not produce acidic drainage during the study period. The tailings consist essentially of quartz, K-feldspar, muscovite and pyrite. The unsegregated tailings amended with very fine limestone displayed the least amounts of pyrite loss whereas those without limestone amendment had the greatest pyrite losses. Predicted onset of acid generation varied from 16 to 75 years for the top sections and in most cases greater than 100 years for bottom sections of the unsegregated tailings with limestone amendments. Unsegregated tailings mixed with fine- and very fine-grained limestone proved to be the most effective in controlling or delaying the onset of acidic drainage under unsaturated conditions.

Jan 1, 2000

By L. K. Nemeth, H. T. Kennedy

The investigation presented in this paper was performd to develop a relationship between the dewpoint pressure of a hydrocarbon reservoir fluid and its composition, temperature and characteristics of the heptanes-plus fraction. This is part of an over-all program to develop correlations for the essential properties of reservoir fluids with the composition, temperature and pressure. In all, 579 dewpoint pressures, determined experimentally on 480 different condensate systems along with their compositions and temperatures, were obtained from the literature and from previously unpublished sources. Compositions were expressed in terms of mol fractions of methane through heptanes-plus, nitrogen, carbon dioxide and hydrogen sulfide, and the molecular weight and specific gravity of the heptanes-plus fraction. Distribution of the samples assured a good representation of most of the major oil-producing areas in the world. A multiple regression analysis program written for the IBhl 7094 digital computer was used to compare numerous equations and to calculate their coefficients. The final equation containing 11 coefficients resulted in an average absolute deviation of 7.4 percent for all the samples. Segregation of data on the basis of one or more variables did not materially improve the results. The correlation developed is useful in predicting the dewpoint pressure of condensate reservoir fluids from variables normally measured in the laboratory. INTRODUCTION In any discussion of the dewpoint of hydrocarbon mixtures, it should be noted that there are two kinds of dewpoints which must be distinguished. The first type, or normal dewpoint, usually occurs at low pressures as dry gas is compressed to the point where liquid first forms. The second type, sometimes called the retrograde dewpoint, occurs when a gas mixture containing heavy hydrocarbons in solution is depressured until a liquid is formed. The first type, as applied to condensate mixtures, would normally be below atmospheric pressure and would be of no interest in reservoir performance. The second type is of great significance in interpreting reservoir behavior and is the property referred to throughout this paper. Laboratory measurement of dewpoints is laborious, expensive and subject to many errors, and it is desirable to find a reasonably accurate method to predict dewpoint pressures from the composition and other readily available properties normally measured on the fluids. A possible method of calculating dewpoint pressures would be to employ a set of equilibrium ratios (K-values). 1 However, the K-values themselves depend on composition as well as temperature and pressure; presently their use adds nothing to the accuracy of predicting dewpoints. If future correlations provide a significantly better method of estimating K-values for heavy hydrocarbons, they may be of greater use. REVIEW OF LITERATURE In 1944, Olds, Sage and Lacey 2 studied the behavior of fluids from the Paloma field. Properties of seven mixtures were studied at temperatures ranging from 100 to 250 F and at pressures up to 5,000 psia. From the information obtained, the influence of composition and temperature upon the dewpoint was determined. It was found that removal of the intermediate molecular weight components from the mixture resulted in considerable increases in the dewpoint pressures. Results indicated that the effect of changes in temperature was relatively minor when compared with the effect of modifying the mixture by removing the intermediate components. Thus, removal of propane and butanes resulted in an increase in dewpoint pressure more than 10 times greater than a change in temperature from 100 to 250 F. The authors stated that althouah

By D. W. Fuerstenau

Recently R. J. Charles1 showed that comminution of brittle or semi-brittle materials in batch operations is described more appropriately by a variable energy relationship than by the specific relationships proposed by Rittinger,2 Kick,3 and Bond.' That is, the value of n in the empirical differential operation which applies to crushing and grinding (Eq. 1) is variable. Independently, Holmes' developed an identical generalized equaton for size reduction. The experimental data of Charles and Holmes show that the value of n is determined by the material and the comminuting machine and is constant for a given combination of these two conditions. The general objective of the present article is to extend the Charles-Holmes concepts to continuous ball milling. The specific objective is to analyze the operation of a vibratory ball mill dry-grinding chromite in a continuous open circuit and to develop an equation for the comminution of chromite in this mill. Basic Principles: In a batch mill the length of time during which the material is ground is a direct measure of the energy expended on the material, except possibly for exceedingly fine grinding. However, in a continuous operation, the fraction of the total expended energy which is useful for grinding will vary according to feed rate and amount of material in the mill. If the amount of material within a continuously operating vibratory mill is low enough so that only part of the expended energy is used for grinding, the extent of size reduction at constant power input must depend upon the length of time the material is retained within the mill, namely, upon retention time. The following analysis pertains to a continuous mill operating under these conditions. The empirical differential equation that applies to the comminution of brittle materials is:" dE = -Cdx/x" [1] where dE is an infinitesimal energy expenditure, C a constant, dx an infinitesimal size change, x the particle size, and n a constant. For continuous grinding in an open circuit at constant power input, P, Eq. 1 must be written as (dtr)P = -C dx/x" [la] where dt, is an infinitesimal time during which a particle of size x is in the mill, and C' is a constant. A ground product never consists of particles of single size but always comprises a distribution of sizes. In comminution, the expenditure of energy causes a lateral shift in the size distribution.', ' " The general objective of any engineering study of comminution is to correlate the magnitude of this size distribution shift with the energy expended, the ultimate aim being to cause the greatest shift with the least amount of expended energy. Although a number of criteria can be used to measure this shift, Schuhmann's size modulus has been found convenient.' Mathematically, the Schuhmann size distribution can be expressed as follows:" y = l00(x/k) [2] or in differential form: dy = [F- xa-' dx ] K, where y is percentage of material finer than size x, a is a constant that determines weight distribution among particles of various sizes, and k the size modulus that denotes the theoretically maximum-sized particle in any size distribution. By considering the energy required to reduce an element of weight of material, dy, from size x, to size x, the element of time during which the material must remain in the mill at at power will be (dt..).= J'-Cax!(dy) [3] Summing up all the elements of weight from zero to 100 for a product that conforms to the Schuhmann size distribution yields C C f Cdx,\( 100«x°-'dx\

Jan 1, 1960

By W. K. Connor, O&apos

Thermal Treatment Technology Division Albany Research Center, U.S. Dept. of Energy Oregon. This evaluation included a characterization study and direct smelting tests conducted in a bench-scale electric arc furnace (EAF). In contrast to other thermal treatment technologies considered for these wastes (i.e., fluidized bed combustion), direct smelting in the EAF can process 100% of the wastes without prior beneficiation, and utilizes solid oxidant additions (in this case iron ore) rather than air to oxidize the carbon. This solid oxidant addition is advantageous because it results in the production of several value-added furnace products. These products include cast iron resulting from the reduction of the iron oxides, baghouse dust containing virtually all of the zinc from the residues, and a clean (nonhazardous) slag product suitable for recycle as concrete aggregate or construction fill. Offgas from the smelting furnace also holds potential as fuel gas for cogeneration. The direct smelting tests conducted thus far were successful at producing the desired furnace products, exhibiting the potential for complete recycle of the waste pile. A cast iron product of comparable quality to conventional cast irons was produced, at nearly 80% iron recovery to the metal. The slag product was determined to be nonhazardous, based on the EPA TCLP. Lead and zinc partitioning to the dust product was greater than 99%. The material balance over the furnace indicates that for every ton of feed processed, 540 lb. of cast iron, 600 lb. of slag, and 150 lb. of dust would be produced. Energy consumption was roughly 1.10 kWxh/lb of feed material. Prior experience suggests that these figures measured in the bench-scale furnace would translate to 0040 to 0.50 kWxh/lb at the industrial-scale.

Jan 1, 2000

By P. Henry

A novel electrochemical cell has been developed for the recovery of MnO2 from residue of pyrolusite ore leading loaded with Fe, Al Ni, Co and Si impurities, This new process can be considered as an alternative to the traditional methods : S02, H2O2 or bioleaching. It has been observed to proceed fairly rapidly and could prove to be a more economically viable process, as well as being more environmentally acceptable. Electrochemical characterization and kinetic studies have shown that MnO2 is effectively leached by electrogenerated ferrous ions at high current density from a pulp containing less than 5 g8 Fe. The chemical reactions are : Cathode (inox) : 2F23+ + 2e ? 2 Fe2+ Bulk: MnO2 + 2 fe2+ 4H+ ? Mn2+ + 2 Fe3+ + 2 H2O Anode (Pb-Ag) : H2O ? ½ O2 + 2H+ + 2e Global: MnO2 +2H+ Fe2+ = Mn2+ + H2O + 1/2 O2 The catholyte (MnO2 pulp) circulates upward in the expanded mesh cathode separated from the sulfuric acid solution anolyte by a separator which shows high mechanical resistance, low porosity, low potential drop, and reasonable cost. Laboratory and mini-pilot tests have led to the construction of an OT crating pilot plant (100 kg/hr) able to leach more than 95% of Mn, Ni, Co at 1000-1200 A/m2, 50°C with high faradic yield (> 95 %) and low power consumption (3.2 kWh/kg kWh/kg &4D). New applications like the treatment of spent Zn-Mn batteries, polluted soils, spent catalysts and oxide ore (cobalt, nickel) with electrogenerated redox species are now investigated at a laboratory and mini-pilot scale.

Jan 1, 2000

By G. M. Steed, A. O. Oyinloye

The deposit lies in amphibolite-facies biotite granite-gneisses of Proterozoic age, 4 km east of a major crustal break known as the Ifewara-Zungeru fault. Gold mineralisation is contained in a zone of quartz-carbonate (mainly calcite) veins and hydrothermally altered gneisses with associated small-scale intrusions along a steeply dipping second-order fault zone that roughly parallels the main fault. Gold is present mainly at grain boundaries between quartz and carbonate as discrete particles up to 100 micrometres in size, in general association with sparse, scattered pyrite, pyrrhotite and some base metal sulphides. Adjacent to the gold-bearing zone the granite-gneisses have been hydrothermally altered with minor volume increase, most notable enrichment being in K2O, S, Pb and Cu (and Au). High concentrations of Th, Y, Ce and Zr in the granite-gneisses imply derivation from S-type granites. It is likely that their high heat production capacity maintained the high temperatures needed to transport gold in the hydrothermal systems. It is most probable that the mineralisation dates from the Pan-African orogeny (650-450 Ma)

Apr 1, 1996

During the summer of 1973 we were asked to perform a theoretical investigation of the propagation of low frequency (LF) radio waves down deep (10,000 feet) hoistshafts* for the case where the hoist cable ("rope") is the only metal conductor present. Propagation is by means of the TEM coaxial mode of transmission in which the hoist cable serves as the inner conductor and the surrounding rock acts as the outer conductor. Since the rock is a relatively poor electrical conductor the current in the outer conductor of the coaxial line is not confined to a very thin surface layer as in a metal coaxial cable, but spreads radially to a distance that is generally many times the shaft diameter. This feature of the wave propagation requires a more sophisticated theoretical treatment than the approximate skin-depth theory that is adequate for metal coaxial lines. In this Part we treat the hoist shaft wave propagation loss, characteristic impedance, and the field current distributions in the surrounding rock medium. We also show that the large penetration of the wave into the rock outer conductor does not present a difficult problem with regard to coupling the transmitter or receiver to the transmission line with a minimum of insertion loss, but that the large impedance mismatch caused by the capacitance termination between the cage and shaft wall may well be the most significant contribution to overall system loss. Inductive coupling and impedance matching to the hoist rope/shaft transmission line are also treated briefly. Preliminary results indicate that a broad minimum in overall system loss should occur between 100 kHz and 1 MHz, possibly centered around 300 kHz. Further work is needed to better quantify this signal loss behavior, compare it with hoist shaft electromagnetic noise spectral data recently acquired by NBS, and identify the most favorable operating frequencies.

Jan 1, 1974

By T Purvis, J Calverd, A-K Greve

The Ernest Henry Mining (EHM) underground mine is situated adjacent to the Great Artesian Basin in North Queensland and within a fracture zone. Underground development commenced in February 2008 and has extended to approximately 1000 vertical metres below the surface.Groundwater has been encountered in numerous locations throughout the mine, predominantly on the eastern side of the orebody and often related to fault structures. Most of the groundwater encountered has been managed with conventional pumping systems; however, on occasions large water inflows have been encountered, which have had a significant impact on the planned development of the mine. Some of the intersections encountered had the potential to compromise the mine from a combination of high temperature (over 45°C), high pressure (3500 kPa) and high flows (50–100 L/s).This paper describes three case studies where significant water inflows were encountered and then controlled by the injection of cementitious grout into the rock mass. The case studies are the 1650 mid-shaft heading, the 1325 shaft access decline and the 1625 to 1475 fresh air rise (FAR) raise bore. Each case study includes a brief description of the event that occurred and the grouting equipment and techniques developed to enable mining to continue.The paper also describes the development of a hydrogeological map of the mine, the probe-hole regime used for high-risk headings and the required processes and systems to inject both cementitious grouts and polyurethane resin into the rock mass.CITATION:Purvis, T, Calverd, J and Greve, A-K, 2014. Management of high-pressure groundwater in underground development at Ernest Henry Mine, in Proceedings 12th AusIMM Underground Operators’ Conference 2014 , pp 217–226 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Mar 24, 2014

By M. N. Shetty

LARGE copper whiskers (-100 p) of 11111 orientation were tested in a floor-model Instron testing machine, at liquid nitrogen temperature. (Testing methods will appear elsewhere.) Whiskers deformed by twinning after some initial deformation. A load-elongation curve at the onset of twinning is reproduced in Fig. 1. Twinning was confirmed by taking a back-reflection Laue picture, using a slit colli-mator, which showed distinct splitting of reflections. The tensile stress reached just before twinning is about 1.4 x 107 g per sq cm (-7.0 x106 g per sq cm—resolved shear stress) which drops to 1.2 x107 g per sq cm (-6 x 106 g per sq cm—resolved). This twinning stress is about five to ten times larger than the value for bulk single crystals of copper deformed at 77°K (-106 g per sq cm—resolved). Twinning models based on Cottrell-Bilby's pole mechanism are discussed in detail by Venables.' In the present work a mechanism based on the idea of failure of a Lomer-Cottrell barrier by recombination will be proposed. An L-C barrier may fail either by recombination or by dissociation.3 Fig. 2 provides the necessary information. It shows that the stress necessary to break such a barrier is about 1.8 x 107 g per sq cm by recombination and 4 x 107 g per sq cm by dissociation at 77°K. The twinning stress reached by whiskers is comparable to the stress level required for failure of an L-C barrier by recombination. (Stroh himself points out that his calculations should not be taken too literally.) We consider a segment of the L-C dislocation which has recombined (AB in Fig. 3) over a length to form the total dislocation which then glides in the

Jan 1, 1965

By C A. Locke, M Stevens, P Vidanovich, J Cassidy, J L. Mauk

The Karangahake adularia-sericite epithermal gold-silver deposit, located at the southern end of the Waitekauri Corridor, Hauraki Goldfield, occurs as quartz veins with associated alteration haloes. Integrated geophysical studies were undertaken to determine the expression, location, and extent of these alteration zones. Aeromagnetic data show an extensive, magnetic æquietÆ zone over Karangahake and the southern Rahu Ridge that represents a zone of magnetite destruction resulting from hydrothermal alteration. Analytic signal data are used to define the boundary of this zone; the resulting 6 km2 area is elongate north-south with an irregular boundary. A detailed gravity survey over the area reveals a positive residual gravity anomaly, up to 30 gu in amplitude, over the Karangahake deposit. Density measurements on near-surface rocks give low values indicating that the source of this positive gravity anomaly must be deep; possible causative bodies include an igneous intrusion or dense sulfide mineralisation. To the west and east of the host Waipupu Formation, strong gravity gradients of 100 gu/km and 65 gu/km reflect the faulted boundary of the Hauraki Rift, and the edge of the Waihi Basin respectively. High resolution airborne radiometric data define a 2.2 km2 area of potassium enrichment. This area is elongate north-south and has an irregular boundary. It coincides approximately with the centre of the magnetic quiet zone and the peak of the gravity high, and correlates with known areas of intense mineralisation. Anomalously high potassium counts and elevated K/Th ratios correlate with areas of potassic alteration that have undergone K-metasomatism. Underexplored portions of this zone may indicate areas of gold-silver prospectivity. Combined geophysical data therefore reveal the extent of hydrothermal alteration, and the central zone of Kmetasomatism that is most likely to contain orebodies.

Jan 1, 2005

By B Mohanty, A Siamaki, K Esmaeili

Large scale open pit mining and quarrying operations dictate safe and reliable pit wall stability. The current approach of employing the particle velocity-scaled charge distance approach to estimate and minimize damage to residential structures is considered inadequate to protect rock slopes. This study utilizes close-in blasting vibration data as input to an advanced 2D numerical code to study its applicability to serve as a predictive tool in terms of blast-induced rock slope failure. Two tri-axial accelerometer stations, consisting of high-frequency and high-amplitude (20 kHz, 100g) sensors, located within ~100m of the blast, but at two different bench levels, were used to monitor production blasts in a limestone quarry. The production blast consisted of double-decked explosive loads in 125 mm (5 in) diameter holes, with an inter-deck delay of 42 ms, and each deck consisting of 130 kg (285 lb) of emulsion explosive. The blasting vibration data obtained at the two bench levels were critically analyzed, and the vibration results served as input to the numerical model consisting of a single rock block with a 45 degree persistent joint plane but with specified strength properties, significantly different from that of the intact rock. The model was able to characterise progressive accumulation of damage in the form of microcracks along the joint surface as a function of the relatively low vibration load from successive explosive decks. The results showed that such a numerical model can serve as a very good diagnostic and predictive tool, when backed up by careful vibration monitoring and further supported by detailed slope monitoring.

Jan 1, 2017

"Large scale open pit mining and quarrying operations dictate safe and reliable pit wall stability. The current approach of employing the particle velocity-scaled charge distance approach to estimate and minimize damage to residential structures is considered inadequate to protect rock slopes. This study utilizes close-in blasting vibration data as input to an advanced 2D numerical code to study its applicability to serve as a predictive tool in terms of blast-induced rock slope failure. Two tri-axial accelerometer stations, consisting of high-frequency and high-amplitude (20 kHz, 100g) sensors, located within ~100m of the blast, but at two different bench levels, were used to monitor a production blasting in a quarry. The production blast consisted of double-decked explosive loads in 155 mm (6 in) diameter holes, with an inter-deck delay of 42 ms, and each deck consisting of 130 kg (285 lb) of emulsionexplosive. The blasting vibration data obtained at the two bench levels were critically analyzed, and thevibration results served as input to the numerical model consisting of a single rock block with a 45 degree persistent joint plane but with specified strength properties, significantly different from that of the intact rock. The model was able to characterise progressive accumulation of damage in the form of micro-cracks along the joint surface as a function of the vibration load from successive explosive decks. The results showed that such a numerical model can serve as a very good diagnostic and predictive tool, when backed up by careful vibration monitoring and further supported by detailed slope monitoring."

Jan 1, 2017

By Peter Hayes

Moonee Colliery operates a longwall extraction system in the Great Northern seam of the Newcastle Coal Measures, approximately 100km north of Sydney, NSW. In the initial mine area of longwall blocks1-4a, the Great Northern seam is overlain by a massive conglomerate approximately 35m in thickness. Unanticipated sudden, blocky caving of this material has produced windblasts with associated velocities of 100m/sec and over-pressures of 35kPa. Although these events have not resulted in fatality, the potential safety risk to face personnel was such that the mine was threatened with closure. The development of a Windblast Management Plan to minimise the exposure to windblasts, a Micro-seismic Management flan to predict caving events, and the use of hydraulic fracturing to generate caving on demand, have all contributed to the salvation of the mine. Prior to the introduction of hydraulic fracturing, falls were highly variable and ranged in goaf area from 2000m2 to 30,000m2 with an average of around 7.000m2. Hydraulic fracturing has introduced consistent and far less variable falls, planned as averaging around 5000m2 and all accompanied by microseismic warning, Moonee Colliery is believed to he the only operation in the world using real-time microseismic warning and using hydrofracturing as a day-to-day operational process. These processes have enabled it to return to financial viability in an environment of strict procedural control, whilst ongoing efforts are made to optimise and enhance these systems. Moonee's story is a case study of the successful application of research and development work to the economics of a mine.

Jan 1, 2000

1. Book reviews Perspectives in metallurgical development. London, The Metals Society. 338 pp. £29. Reviewer: John V. Bee Mechanics of oil shale, edited by K.P. Chong and J.W. Smith. London, Elsevier Applied Science Publishers Ltd, 1984. 603 pp. £75. Reviewer: R.W.O. Kersten 2. Recent publications CANADIAN MINERAL POLICY SECTOR. Metallurgical works in Canada. Primary iron and steel 1984. Mineral Bulletin MR 203. Ottawa, Canadian Government Publishing Centre, Supply and Services, 1985. $6.00. Tin and its uses no. 143. Greenford (England), International Tin Research Institute, 1985. Mining 1985, edited by Diana Russell. Harlow England), Longman Group Ltd, 1985. 540 pp. £46. The following books are available from CRC Press, Inc., 2000 Corporate Boulevard N.W., Boca Raton, Florida 33431, U.S.A. Inorganic ion exchange materials, edited by A. Clearfield. 304 pp. $100. Polyurethane foam sorbents in separation science, by T. Braun. $80. Advanced particulate morphology: theory and practice, by J.K. Beddow and T.P. Melloy. 208 pp. $79. CRC handbook of atomic absorption analysis, edited by A. Varma. 2 vols: vol. I $114, vol 11 $102. CRC handbooks of inorganic elecrochemistry, edited byL. Meites, P. Zuman, E.B. Rupp, andA. Narayanan. 3. Mintek reports Report M169 The preparation of three South African coals for as reference materials. Report M190 The preparation and certification of a South African phosphate concentrate for use as a reference material. Report M191 The agglomeration of fine material for bacterial heap leaching. Report M197 A computer programme to monitor the performance of an X-ray-fluorescence spectrometer. Metallurgical award The 1984 Acta Metallurgica Gold Medal has been awarded to Professor John W. Christian of Oxford University. The medal is an international award that was established in 1974 to recognize outstanding ability and leadership in materials research. Proterozoic volcanic suites An international symposium will be held at the British Geological Survey, Keyworth, Nottingham, U.K., from 2nd to 5th April, 1986. Entitled 'Geochemistry and Mineralisation of Proterozoic Volcanic Suites', this special meeting of the Geological Society will discuss the geochemical evidence for the nature of volcanism during the Proterozoic. Powder metallurgy Every second year the International Powder Metallurgy Conference, the world's leading event in powder metallurgy, is organized and held alternately in North America and Eruope.

Jan 1, 1985

By Joseph R. Stephens

Deformation substructures of' polycrystalline tungsten, W-2, 9, and 24 pct Re, and W-3 pct Ta were studied by tra?zsrnission electron microscopy. The stress-strain curve for unalloyed tungsten showed gradual yielding followed by work-hardening. Electron nzicrographs indicated a gradual increase in dislocation density with increase in strain up to 5.0 pct. Dislocations, although frequently jogged, were straight over moderate distances and were in a randorn array. Stress-strain curves for alloy specimens of W-2 and 9 pct Re and W-3 pct Ta exhibited a drop in stress at yielding followed by only slight work-hardening. Electron micrographs of these specimens after strains of 0.05, 0.1, and 0.5 pct revealed no change in dislocation substructure from the unstrained specimens. After 2.0 pct strain, the three alloys exhibited dense networks. W-3 pct Ta was characterized by straight, frequently jogged dislocations comparable with the dislocation structure in unalloyed tungsten after a similar amount of strain. In contrast, W-2 pct Re exhibited dislocations that contained widely spaced jogs, while W-9 pct Re had developed a cell structure after the relatively srnall strain of 2.0 pct. The W-24 pct Re alloy contained a few dislocations after 0.1 pct strain, while after 0.5 pct strain twins were evident. Dislocation slip bands apparently preceded the twins. The stress-strain curve for the alloy indicated that twinning commenced after approximately 0.25 pet strain. These results indicate that the primary effect of low rhenium concentrations (2 and 9 pct) in tungsten is to increase dislocation multiplication after macroyielding by reducing the Peierls-Nabarro force (lattice resistance to dislocation motion). The dislocation bands that precede twins in W-24 pct Re may be caused by localized internal stresses resulting fro a metastable structure, for example, clustering of rhenium atoms. The effect of high rhenium additions (22 a 65 pet* Rproperties of tungsten. Klopp, Witzke, and Raffo5 reported bend transition temperatures as low as -100°F (200°K) for dilute electron-beam-melted W-Re alloys tested in the worked condition. Recrystalliza-tion increased the bend transition temperature, but alloys with 2 to 4 pct Re were still markedly superior to unalloyed tungsten. Fractographic examinations of tungsten and W- 3 pct Re and W- 5 pct Re alloys by Gilbert 6 revealed that these low rhenium alloys showed a greater tendency toward cleavage failure than did tungsten. Garfinkle 7 showed that rhenium additions, up to 9 pct, to (100) oriented tungsten single crystals increased the proportional limit stress and decreased the flow stress and the rate of work-hardening. In addition, while deformation in unalloyed (100) oriented crystals apparently involved both (110)100) and (112) slip, crystals with rhenium contents of 5 andpct or more deformed primarily by (112) slip. The mechanism by which high and low rhenium additions affect the mechanical properties of tungsten is still not well-established. The present investigation was undertaken to determine by transmission electron microscopy the effects of low rhenium additions, 2 and 9 pct, and a high rhenium addition, 24 pct, on dislocation substructure in the early stages of deformation of polycrystalline electron-beam-melted tungsten. Unalloyed tungsten and a W- 3 pct Ta alloy were included for comparison. EXPERIMENTAL PROCEDURES Materials. Triple electron-beam-melted tungsten, W-2, 9, and 24 pct Re, and W- pet Ta were used for this investigation. Chemical analyses of the cast ingots are given in Table I. A description of the starting metal powders and melting and fabrication pro-cedures for unalloyed tungsten and the W-Re alloys is reported.5 The W-3 pet Ta alloy was processed in a similar manner. Compression specimens measuring 0.300 in. (7.6 mm) in length by 0.130 in. (3.3 mm) in diam were machined from swaged rods. All alloy specimens were annealed in a vacuum of 8 x 10- 6 Torr (10'2iVper sq m) for 1 hr at 3600°F (2255°K). The recrystallized grain size ranged from 0.06 to 0.08 mm diam for the alloy specimens. Unalloyed tungsten was annealed at 2400° F (1589°K) for 1 hr to produce a recrystallized grain diameter of approximately 0.12 mm. Specimens were electropolished in a 2 pet NaOH solution to a diameter of 0.125 in. (3.18 mm) to remove surface notches resulting from grinding and to improve reproducibility of t data. The ends o the compression specimens were ground flat, parallel to each other, and perpendicular to the longitudinal axes with 4/0 emery paper. Compression Tests. The compressive stress-strain apparatus used for compression tests is described in detail by Stearns and Gotsky.9 Room-temperature compression tests were conducted at a crosshead speed of 0.01 in. per min (0.25 mm per min).

Jan 1, 1969

By Amitava Gangulee, Michael B. Bever

The effects of changes in short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions have been investigated. The heats of formation at 273°K of several alloys after two different thermal treatments were measured by liquid metal solution calorimetry. Their electrical resistivities were measured at temperatures ranging from 4° to 773°k. Tensile tests and microhard-ness measurements were carried out at room temperature. An effective short-range order parameter and an effective interaction energy are defined. The measured changes in the properties are interpreted in terms of these quantities. The short-range order parameter is evaluated separately from calorimetric and X-ray data; the results are in fair agreement. Increasing short-range order lowers the resistivity of- the silver-rich Ag-Mg alloys but does not measurably affect the temperature dependence of the resistivity. Short-range order increases the yield stress of these alloys but does not affect the ultimate tensile stress. Changes in the effective short-range order parameter independently obtained from measured changes in the heat of formation, resistivity, and yield stress are in fair agreement. THE thermodynamic, electrical, and mechanical properties of solid solutions have been investigated as functions of composition in many alloy systems, but the effects of configurational variables, such as short-range or long-range order, on these properties have received much less attention. The silver-rich terminal solid solutions in the system Ag-Mg are well-suited for the investigation of the effects of order. The composition of these solid solutions may be varied over a range extending to about 27 at. pct Mg.1 Appreciable short-range ordering is likely to take place in these solid solutions; the degree of short-range order can be varied by suitable thermal treatments. In the alloy Ag3Mg long-range ordering is possible.2 This paper is primarily concerned with the effects of short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions.-The long-range ordering transition is the subject of a concurrent paper.3 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Specimens. Ag-Mg alloys containing up to 26.4 at. pct Mg were prepared by melting 99.99 pct pure Ag (obtained from Baker Chemical Co.) and 99.99 pct pure Mg (obtained from Eastman Chemi- cal Co. or Johnson Mathey & Co.) in graphite crucibles under molten potassium chloride. The solidified ingots were homogenized at 823°K for 10 days in evacuated Vycor capsules. A surface layer 6 in. thick was then removed by machining. The ingots were swaged into rods (2.5 mm diam) which were drawn into wires (1.0 mm diam). The wire specimens were annealed at 773°K for 24 hr in vacuum and either quenched into iced brine or cooled to room temperature over a period of 15 days. The average grain diameter (obtained from the linear intercepts) was about 0.1 mm. 1.2) Calorimetry. The heats of formation of the alloys were measured in a tin solution calorimeter as the difference in the heat effects of alternate additions of samples of an alloy and the mechanical mixture of its component elements. The additions were made from 273°K to the bath at about 623°K. The heat effect on addition of the alloys was approximately 5.5 kcal per g-atom. The procedure and the method of calculation have been described.4 1.3) X-Ray Diffraction. Short-range order parameters of two alloys were calculated from diffuse scattering intensities,' obtained with briquettes made from powdered specimens. A GE-XRD 5 diffractometer with filtered copper radiation was used. The absolute intensities were based on calibrations with paraffin. 1.4) Resistivity Measurements. The electrical resistivities were measured by a potentiometric method in which the potential drop across the specimen was compared with that across a standard resistance. For measurements below room temperature, the specimens were immersed in liquid helium (4°K), liquid nitrogen (78°K), dry ice and trichloroethylene (195°K), or ice and water (273°K). Measurements above room temperature were made on specimens held in a furnace under helium or in vacuum. The resistivity measurements were reproducible to ±0.5 pct or less. 1.5) Mechanical Tests. Tensile tests were carried out at room temperature with a Tinius-Olsen XY elec-tromatic Universal testing machine. Wire specimens (nominal gage length 1 in.) were used. The strain was measured with an extensometer, which had a sensitivity of 4 x 10-5; the strain rate was 10-3 min-1. Microhard-ness measurements were made with a square-pyramid indenter and a 100-g load.11 2) RESULTS AND DISCUSSION All measurements were made on two parallel sets of specimens, one quenched and the other slowly cooled from 773°K. The reported values are the averages of at least three measurements. In the range of magnesium concentration substantially below that of the composition Ag3Mg, quenched alloys have less short-range order than slowly cooled alloys. As the magnesium concentration approaches that of Ag3Mg, slow cooling develops long-range order. Quenching sup-

Jan 1, 1969

By R. Gibala

Internal-friction measurements on hydrogen-charged iron over the temperature range 4° to 300°K are reported. Two relaxation peaks, the hydrogen Snoek peak at 48 °K and the hydrogen cold-work peak in the range 145" to 2200K, are observed at 80 kc per sec. The effects of hydrogen-charging, aging, and deformation on the internal-friction results are determined and are used to show evidence of partitioning of hydrogen between solid solution and dislocations. The hydrogen-dislocation binding energy is estimated from the behaviors of the relaxation tiwzes and relaxation strengths of the Snoek peak and the cold-work peak. Its value is approxi,mately 6400 cal per mole. MANY investigators have demonstrated the usefulness of internal-friction measurements in determining the manner in which interstitial impurities interact with dislocations in bcc metals. Part of this success has resulted from the existence in bcc interstitial alloys of two anelastic relaxation peaks—the Snoek peak' and the cold-work or Koster peak2 (designated hereafter by SP and CWP, respectively). The SP has its origin in the redistribution of interstitials in solid solution among sites made energetically nonequivalent by an applied stress. The rate at which the redistribution occurs, measured by the relaxation time for the process, is related in a simple way to the diffusion rate of the interstitial in the free solution. The relaxation strength is proportional to the concentration of interstitial in solid solution. The CWP appears to have its origin in the relaxation of an interstitial-dislocation complex for which the relaxation time at a given temperature is much longer than that for the SP. The relaxation strength depends strongly on the concentration of interstitial and the amount of deformation at relatively low concentrations and deformations.2-8 From the dependence of the relaxation strength on interstitial concentration, the SP and CWP may serve as measures of the concentrations of interstitials in free solution and bound at dislocations, respectively. Thus their behaviors have been used to investigate interstitial-dislocation interactions in Fe-C, Fe-N, and several refractory metal systems.'-' However, the Fe-H system has not been studied extensively,? even though disputes in recent years over the mechanism of hydrogen embrittlement in steels involve argument over the extent to which lattice hydrogen and hydrogen-dislocation interactions play an important role.?-'' Previous work on Fe-H indicates the internal-friction behavior to be qualitatively consistent with that for other systems. Apparently, both a SP and a CWP are observed in the temperature ranges 30" to 50°K and 100°to 140°K, respectively (at 1 cps). However, there is neither sufficient nor accurate enough information to identify convincingly these peaks with their supposed counterparts in other systems. Nor have there been any attempts to make quantitative use of these peaks to study hydrogen diffusion, aging, or interaction processes. In this paper, an attempt is made to obtain more complete information on internal friction of hydrogen in iron than presently available. Internal-friction measurements in the range 4° to 300°K on hydrogen-charged iron show that the two peaks discussed above are in fact the hydrogen SP and CWP. Several effects of hydrogen charging, aging, and deformation on these peaks are observed and are used to determine the partitioning of hydrogen between solid solution and dislocation sites in iron. EXPERIMENTAL Materials. The starting material for this investigation was a high-purity iron supplied by National Research Corp. as a 1-in.-diam rod. The following analysis was given (inwt pct): C, 0.004; N, 0.0003; 0, 0.007; P, 0.002; S, 0.005; Si, 0.006; Mn, 0.001; Cu, 0.002; Ni, 0.005; Cr, 0.001; Mo, 0.001. After an initial vacuum anneal (-5 XTorr) at 700°C, the rod was cold-

Jan 1, 1968

By N. Jaffee, J. E. Dorn

An activation energy of 27,400 5 1000 cal per mole was obtained for the creep of poly crystaLline aluminum over the temperature range of 273° to 350°K, at strains varying from 0.003 to 0.230. Stresses varied fronz 2250 to 6000 psi, strain rates from 0.1145 x 10-5 to 29.5 x 10~s min.-1. A strain temperature-compensated time correlatzon was oblained indicating that the structure was depedent solely upon the strain at a given stress; X-ray diffraction analyses and tensile tests on precrept specimens verified this. PREVIOUS investigations1 have revealed that the apparent activation energies for creep of high-purity polycrystalline aluminum are insensitive to the applied stress, strain, and strain rate. On the other hand, the apparent activation energy is dependent on the temperature1,2 as shown by the data reproduced in Fig. 1. Each plateau of this curve is associated with a unique rate-controlling dislocation mechanism for thermally activated creep. It is now very well-established that over the high-temperature range, where the activation energy is about 35,500 cal per mole, the creep rate is controlled by the dislocation climb mechanism. 3 Over the intermediate range of temperatures, from about 260° to 370°K, another unique activation energy, namely 28,000 cal per mole, is obtained. Current evidence strongly supports the contention that cross slip is the rate controlling mechanism for creep in this case: 1) Crystal recovery can occur by a number of mechanisms prominent among which are climb and cross slip. Astrom,4 using the Borelius micro-calorimeter, reported rapid crystal recovery of cold-worked polycrystalline A1 at 340° to 370°K giving an activation energy of 28,000 cal per mole and additional recovery at 455° to 478°K giving an activation energy of 3 6,000 cal per mole. Whereas the latter recovery process was clearly associated with the dislocation climb mechanism, the former, 28,000 cal per mole process could have arisen as a result of the cross-slip mechanism. 2) Single crystals of high-purity A1 favorably oriented for octahedral glide exhibit an activation energy for creep of about 3400 cal per mole over the range from 0° to 400°K and that of about 28,O:O cal per mole over the range from 600° to 775°K . Whereas the lower activation energy process is accompanied by the development of sharp slip-band traces, the 28,000 cal per mole process was uniquely characterized by extensive cross slip. 3) Theoretical calculations by Seeger and schoeck6 suggest an apparent activation energy for cross slip in A1 of about 24,000 cal per mole and another theoretical estimate by Friedel 7 gives the observed 28,000 cal per mole as the theoretical activation energy. It is therefore consistent with this evidence to, at least tentatively, ascribe the 28,000 cal per mole creep process in A1 to the operation of cross slip as the rate controlling mechanism. Although creep has been rather well-explored in the dislocation climb range, very little, excepting perhaps the activation energy, is known about creep in the cross slip range. This investigation was undertaken, therefore, to reconfirm the activation energy for creep in polycrystalline A1 in the intermediate temperature range and to study the strain-time relationship for creep at a constant stress in the cross slip region. EXPERIMENTAL PROCEDURE AND TECHNIQUE The three types of high-purity A1 alloy specimens described in Table I were used in this investigation. Specimens were milled from 0.100 in. thick cold-rolled sheets with their tensile axes in the rolling direction following which they were given a recrys-tallization and grain growth heat treatment at temperatures well above those which were subsequently employed in the creep tests.

Jan 1, 1962

G. D. Kneip, Jr., and J. 0. Betterton, Jr. (Union Carbide & Carbon Corp., Oak Ridge, Tenn.)—The authors have contributed to the theory of zone melting by considering the effects of the solidification of the final zone on the distribution curves for the finite length bar. However, they do not consider in sufficient detail the restrictions imposed by the particular metals involved. Eq. 4 has the analytical solution which is equivalent to Pfann's' equation for normal solidification of the final zone. For distribution coefficients less than one, it is apparent from this form of the equation that, as the solidification approaches completion, the concentration attains extremely large values which are inconsistent with the density of physical materials. The necessary restrictions then are that the solute concentration cannot exceed the density of the alloy, or more frequently, the solubility limit in the solid phase. Secondly, the distribution coefficient cannot be constant from 0 to 100 pet solute unless the liquidus and solidus coincide over this whole region. It would thus be more correct to impose limits on the solubility such as would be indicated by a typical eutectic diagram. Furthermore, in this case the assumption that the distribution coefficient remains constant is more likely to be realized. Eq. 4 should then be replaced by the following C,,(x) =k/L-x [ ?11 3 C11 (x)Ddx - ?11 4 Cn(x)dx= k[Cn (L-l)/k] [ L-x/l]x-1 L-l = x = L-l [kCenterlie/Cn (L-l)]1/k-1 The typical shape for the distribution curve in the final zone is indicated schematically in Fig. 12 for the simple eutectic case. The solidification proceeds according to Pfann's' expression until the concentration reaches the maximum solubility in the solid phasc. At this point, the concentration changes abruptly to the eutectic composition and remains at this value for the duration of the solidification. The width of the flat region, and the back reflection of this effect into the concentration curve on subsequent passes, depends upon the ratio of the eutectic concentration to the original concentration, upon the distribution coefficient, and upon the number of passes. Similar effects on the concentration curves in the first zone length would be expected in many systems for which the distribution coefficient is greater than one, and where the maximum solubility is not too much larger than the original concentration. The discussers agree with the authors that the assumption that the liquid is uniform in concentration should be considered with caution. Kneip and Better-ton' have shown, however, that in floating zone refining of zirconium, using induction heating, the distribution of iron agrees with theory which assumes a uniform liquid composition. Hence, in this case, the experimentally realized distribution coefficient agrees with the present phase diagram within the experimental uncertainty. L. Burris, Jr., C. H. Stockman, and I. G. Dillon (authors' reply)—The authors are happy to have received the comments of G. D. Kneip, Jr., and J. 0. Betterton, Jr., which provide additional insight into the zone refining process. It is true that the equations developed are inapplicable if the solute solubility in the solid phase is exceeded. However, this restriction on the use of the equations was clearly stated in the paper. A closer approach to

Jan 1, 1957