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By J. H. Smith, H. W. Paxton

ALTHOUGH many structural and kinetic investigations have been made for alloys of iron and nickel, only meager data exist from thermodynamic investigations. The purpose of this note is to estimate the free energy of the Fe-Ni solid solutions from thermodynamic data available for ternary alloys containing iron and nickel. The lack of a description of the thermodynamic behavior for the Fe-Ni system has required the structural and kinetic analyses of the system to assume some form of solution behavior, usually regular, e.g., the mar-tensite transformation analysis of Kaufman and Cohen, 1 consistent with the limited thermodynamic data. Indications that this system could exhibit ideal solution departures might have been suggested by the large deviations from additivity rules observed in the density and lattice-parameter measurements of Jette and Foote2 who interpreted this in terms of possible solute-solvent interactions. Later Turkdogan et al. 3 and more recently Ward and wright 4 found a minimum in the graphite solubility in liquid Fe-Ni solutions near the concentration of FeNi3 with deviations from linearity persisting at all concentrations. This was interpreted by Ward and wright4 to indicate negative heats of solution and was suggestive of short-range ordering. The infinitely dilute activity coefficient of carbon (?oC) was also observed by smith5 to pass through a maximum near the FeNi3 concentration in Fe-Ni solid solutions. Recent investigations of the liquid solutions over the entire concentration range by Zellars et a1.' and Speiser et a1.," using vapor-pressure determinations, revealed both negative departures from Raoult's law and a nonregular solution behavior. The solid alloys have been studied by Oriani 8 and Kubaschew-ski and von Goldbeck6 employing gaseous H2/H2O equilibria with Fe and FeO. Both investigations were in substantial agreement, indicating very small departures from ideality. However, Oriani observed the formation of Fe3O4 (instead of FeO) at XFe= 0.441 which severed the equilibrium and precluded experimental investigation of the nickel-rich alloys. Heat-capacity and heat-content measurements have been evaluated by Montgomery10 and found generally unsatisfactory for gleaning thermodynamic information. This is due to the unknown final states of the alloys caused by the interference of the martensite transformation on cooling iron-rich concentrations and superlattice formation, magnetic transformation, and the varied heat treatments used by investigators of nickel-rich concentrations. As an alternative to the experimental difficulties, indirect estimates of the solid-solution behavior have been made by Fleischer and Elliott11 and Smith et a1.12 From their measurements of the solubility of Fe-Ni alloys in liquid lead, Fleischer and Elliott calculated the nickel activity (aNi) (and integrated for aFe) by assuming: 1) liquid lead has no solubility in solid Fe-Ni alloys, 2) Henry's law is obeyed throughout the liquid lead-rich phase (0— 12 at. pct Nil, and 3) Henry's law constant is independent of relative iron and nickel concentrations. The estimate of Smith et a1.12 was obtained

Jan 1, 1964

By B. M. Larsen, T. E. Brower

In two previous paperslJ dealing with the carbon-oxygcn reaction, and the simultaneous content of each, in liquid steel in the furnace, we have made use of the quantity A[O], defined as the excess oxygen beyond what would be in equilibrium with carbon then present if the pressure of carbon monoxide were I atm.; that is, if [C] X [O] is taken as 0.00222, A[O] = [O] - 0.0022[C] where [O] is the percentage of oxygen by weight as measured by the method described earlier.3 This quantity ?[O] proves to be substantially independent of carbon content over the range 0.08 to I,z per cent, as well as of the basicity of the slag, and is nearly always within the limits o.o15 to o.oz5 per cent when the bath is boiling normally and is in what we have termed a steady state, Apparently it must be at least about 0.014 per cent before boiling occurs; but this threshold value seems to depend upon the ease of bubble formation at the metal-hearth interface, hence upon the condition of the surface of the hearth. In any case, ~(01, on the average, changes considerably following any disturbance of the bath, as by addition of ore. The present paper deals with the average changes in A[O] level following addition of spiegel or crop ends, or after procedures to promote stirring, or by tapping of the steel from the furnace. The observations were made on a large number of commercial heats, and consequently are subject to the influence of various disturbing factors; the results have the compensating merit of showing the consistency obtainable under the limitations imposed by practical operation. Variability of Excess Oxygen in Normal Open-hearth Operation The preceding genera' statements refer to the average value of A[0] particularly in heats that are boiling actively; on individual heats, which are less active, there may be a variable time lag between the disturbance and its effect, which complicates the interpretation of what is going on. For instance, if in the normal refining process boiling is sluggish, the slag usually is gaining Oxygen from the gas phase above it, Or from added Ore$ faster than it is losing oxygen to the metal; Yet when the bath starts to boil vigorously, the opposite condition may prevail for Some time. The consequence of this lag is a variation of A[o], the interpretation of which in a sing1e heat may not be immediately obvious. This condition is illustrated in Figs. I and 2. In Fig. 1, A[0] at the beginning of the test period was near the lower limit of its usual range (dashed lines) in the steady state as a consequence of the lime boil, which had ended about as indicated. The bath is now cold, carbon drop is slow, and the first small orc feed causes only a small rise in A[O]; as the temperature rises and as lime dissolves in the slag, and the bath becomes more active, the

Jan 1, 1948

By Bernt Ellingsaeter, Terkel Rosenqvist

IN the silicothermic reduction of magnesia, burned dolomite is treated with high grade ferrosilicon in an evacuated steel retort at temperatures between 1150° and 1200°C. The following reaction is assumed to occur MgO + CaO + 1/2 Si (Fe) - Mg(g) +- & Ca,SiO, + Fe with the equilibrium constant on the basis of thermodynamic data for the substances involved and assuming unit activity for all solid constituents, Kubaschewski and Evans' calculated the magnesium pressure as a function of temperature logp,, (mmHg) = 15.06-1.61 T- log T- 13,16O/T. Pidgeon and King," who measured the magnesium pressure by means of a flow method, found values about three times the calculated ones. This may be caused by uncertainties in the thermodynamic data, but may also be caused by the formation of other reaction products, such as Ca,SiO,, which is known to be the stable silicate in equilibrium with lime. Whatever the exact reaction may be, it is evident that as long as all other factors are maintained constant the magnesium pressure will vary with the silicon activity, viz: p,, = &,. (p,,) ", where (p,,)" is the magnesium pressure by the reduction with silicon of unit activity. In the present investigation, p,,, was therefore measured for various grades of ferrosilicon and their silicon activities were calculated. The experimental method was similar to that used by Pidgeon and King. Briquettes of burned dolomite and Fe-Si alloys were placed in a 1 in. heat resistant steel tube and were heated to 1200°C. By means of a flow of purified hydrogen, the magnesium vapor was swept into a condenser filled with steel wool. From the amounts of hydrogen used and magnesium condensed the magnesium partial pressure was calculated. First a tube of 28 pct Cr steel, and later a tube of Kanthal D (a ferrous alloy with 22.6 pct Cr, 2 pct Co, and 4.5 pct Al), was used as a heat resistant tube. The latter tube showed the best heat resistance. The dolomite used had the following composition: 43.6 pct MgO, 55.5 pct CaO, 0.2 pct K,O + NalO, 0.2 pct Fe,O,, and 0.3 pct insoluble. The ferrosilicons were prepared from 98 pct Si of technical grade (0.7 pct Al, 0.3 pct Ca, and 1 pct Fe) by melting with various amounts of electrolytic iron of high purity. The alloys thus obtained were analyzed on their iron and silicon contents, which added up to between 99 and 100 pct. The amounts of reactants were chosen so that there would always be an excess of the oxides, and the average decrease in silicon content during the experiments would be about 1 pct. Most of the reaction occurred in the part of the reaction mixture facing the gas flow. The change in the silicon concentration in the part facing the condenser was, therefore, negligible. To facilitate the reaction, about 1 pct fluorspar was added to the briquette mixture. Fluorspar does not enter the reaction, but is known to act as a

Jan 1, 1957

By B. M. Larsen, T. E. Brower

In two previous paperslJ dealing with the carbon-oxygcn reaction, and the simultaneous content of each, in liquid steel in the furnace, we have made use of the quantity A[O], defined as the excess oxygen beyond what would be in equilibrium with carbon then present if the pressure of carbon monoxide were I atm.; that is, if [C] X [O] is taken as 0.00222, A[O] = [O] - 0.0022[C] where [O] is the percentage of oxygen by weight as measured by the method described earlier.3 This quantity ?[O] proves to be substantially independent of carbon content over the range 0.08 to I,z per cent, as well as of the basicity of the slag, and is nearly always within the limits o.o15 to o.oz5 per cent when the bath is boiling normally and is in what we have termed a steady state, Apparently it must be at least about 0.014 per cent before boiling occurs; but this threshold value seems to depend upon the ease of bubble formation at the metal-hearth interface, hence upon the condition of the surface of the hearth. In any case, ~(01, on the average, changes considerably following any disturbance of the bath, as by addition of ore. The present paper deals with the average changes in A[O] level following addition of spiegel or crop ends, or after procedures to promote stirring, or by tapping of the steel from the furnace. The observations were made on a large number of commercial heats, and consequently are subject to the influence of various disturbing factors; the results have the compensating merit of showing the consistency obtainable under the limitations imposed by practical operation. Variability of Excess Oxygen in Normal Open-hearth Operation The preceding genera' statements refer to the average value of A[0] particularly in heats that are boiling actively; on individual heats, which are less active, there may be a variable time lag between the disturbance and its effect, which complicates the interpretation of what is going on. For instance, if in the normal refining process boiling is sluggish, the slag usually is gaining Oxygen from the gas phase above it, Or from added Ore$ faster than it is losing oxygen to the metal; Yet when the bath starts to boil vigorously, the opposite condition may prevail for Some time. The consequence of this lag is a variation of A[o], the interpretation of which in a sing1e heat may not be immediately obvious. This condition is illustrated in Figs. I and 2. In Fig. 1, A[0] at the beginning of the test period was near the lower limit of its usual range (dashed lines) in the steady state as a consequence of the lime boil, which had ended about as indicated. The bath is now cold, carbon drop is slow, and the first small orc feed causes only a small rise in A[O]; as the temperature rises and as lime dissolves in the slag, and the bath becomes more active, the

Jan 1, 1948

By Ervin E. Underwood

IT has been recognized for many years that dis-persed particles have great value in raising the creep resistance of metallic alloys. In fact, some of the most successful high-temperature alloys owe their superiority to this factor above all others. A recent observation by Glen1," indicates that even better high-temperature resistance to deformation results in alloys capable of two successive precipitation reactions. The ramifications of this finding are of great interest. Unfortunately, our understanding of the reasons for such notable improvements has not kept pace with technical developments. In an effort to uncover some of the basic facts governing strengthening by particles, a program was initiated at the Battelle Memorial Institute with the primary goal of comparing creep strengths in single-phase and two-phase (precipitating) alloys. The effects of precipitation from solid solution on the creep properties of alloys are generally such that the resistance to creep is increased. However, if alloys are heat treated to different degrees of hardness before creep testing, it is often found that those possessing the maximum hardness initially do not necessarily have the maximum creep resistance. Depending on the stresses and temperatures involved other structures may prove more desirable. Considerations of the above nature indicate the importance of defining the initial state of the alloy. Here, it was decided to start with quenched single- phase alloys in which precipitation and creep deformation proceed concurrently. Equipment and Experimental Procedures Preparation of the Specimens—Four 25 lb ingots were prepared from 99.999 pct Cu and 99.996 pct Al to compositions of 1, 2, 3, and 4 wt pct Cu. Spec-trographic and chemical analyses are listed in Table I. After heat treatments and intermediate reductions, the alloys were cold rolled to 1/8 in. thick sheet. The final cold reductions amounted to 50, 40, 20, and 10 pct for the 1, 2, 3, and 4 pct Cu alloys, respectively. The specimens for creep testing were machined into tensile flats 7 in. long, 3/4 in. wide (at the shoulders), and 1/8 in. thick. The reduced sections were 1/4 in. wide and 21/2 in. long. After heat treatments at 540°C to an ASTM grain size of 1 1, the specimens were quenched into water at room temperature, then electropolished in a glacial acetic acid and perchloric acid solution. The gage marks were Knoop impressions placed 2 in. apart on the reduced sections. Blanks of 1 x 1 in, were cut from the same sheets for the age hardening runs and were given the same grain size heat treatments. The specimens and blanks were stored in a refrigerator at —40°C until needed for testing. Creep Measurements—Creep tests were conducted in a constant temperature room which was maintained at 26° ±1°C. A split-type, hinged, vertical-tube furnace was mounted on a horizontal track so that the specimen could be enclosed suddenly. Thus, it took about 15 min for the specimen to come within 5°C of the test temperature. The temperature variation along the specimen was controlled to about

Jan 1, 1958

By M. C. Flemings, P. J. Ahearn

Dendvite morphology of unidirectionally solidified Sn-12 pct Bi alloy was determined with the aid of X-ray and macroetch techniques. Columnar growth direction (growth direction of primary arms) in this alloy is [110]; secondary arms grow in the [lii], [111), and [112] directions. Interstices between [112] dendrite arms fill in during early stages of solidification so that well-defined (110) planes are seen in the final structure (parallel to the heat-flozo direction). Similarly, interslices betweex the [111] secondary arrlls fill in to form (112) planes, and interstices between [1111 ] arms fill in to form (112) planes. DENDRITE morphology in alloys is conveniently studied in unidirectionally solidified castings. In this type of solidification, heat is extracted from a single chill surface of the casting while other surfaces are insulated. Solidification progresses from the chill and results in cast grains that are columnar with the long axis of the grain perpendicular to the chill. Dendrite morphology is conveniently studied by examination of etched surfaces parallel and perpendicular to the chill, as previously described.'" Experimental studies on the growth direction for tin are in general agreement. The major growth direction is [110]:-' although this is altered somewhat by supercooling. In one study, tin dendrites pulled from a supercooled melt had a growth orientation 12 deg away from the [110] direction toward the [002] direction.' This orientation could be changed back to the [110] or close to the [110] direction by changing the tempera- ture gradient in the melt. In a study using autoradio-graphic techniques, (111) directions were shown to be directions of preferred growth in addition to the [110) direction.7 PROCEDURE The samples employed in this study were cut from 12 pct Bi-88 pct Sn castings, 1.5 in. in diam and 3.5 in. tall. The casting procedure consisted of heating the charge to 390°C and then pouring the molten alloy directly into a gypsum sleeve mounted on a massive copper chill. Specimens were cut from the ingot, mounted, polished, and etched with Taffs reagent [FeC13 .6H2O, 2 g; HC1, 5 cu cm;H20, 30 cu cm; CzHaOH (95 pct), 60 cu cm].' The dendritic pattern was clearly visible after etching. Photomicrographs at about 8 and 35 times were taken on surfaces parallel and perpendicular to the chill. Laue back-reflection patterns were obtained from three different columnar grains in a singIe polished face 2 in. from the chill. The cut face was polished and positioned in the beam of a Laue camera, so that diffraction occurred from a single dendritic grain. The resulting diffraction pattern was interpreted to determine crystal log raphic orientation in relation to the heat-flow direction and in relation to microstruc-ture of the given grain. RESULTS Fig. 1 shows a horizontal and vertical section of the columnar structure, at low magnification. Light regions are rich in tin, and darker regions tin-poor; the primary phase is tin-rich a phase. The two sections shown were taken orthogonally from the same metallographic specimen. It is readily seen from Fig. 1 that the dendrites have

Jan 1, 1968

By Michael Hoch, Seong Kwan Rhee

The ternary system Zr-Cr-0 was investigated at 1200°, 1500°, and 1700°C. The isotherms at these temperatures were determined by metallographic and X-ray diffraction analysis of carefully selected alloys. AS a part of a series of investigations1-4 of the ternary and quaternary phase diagrams on refractory metals and their compounds, the ternary system Zr-Cr-O was investigated at 1200°, 1500°, and 1'700°C. The binary diagrams Zr-Cr, Zr-O, and Cr-0 as reported by Hansen5 and Levin et a1.' and the existence of a ternary coompound ZrsCrsO (q-carbide structure a. = 11.96A) provided a good base for this investigation of the Zr-Cr-O phase diagram. MATERIALS The materials used and their suppliers were: Zirconium powder, 99.4 pct pure, Charles Hardy, New York; Zirconium dioxide, Fairmount Chemical Co., Newark, N.J.; Chromium powder, 99.85 pct pure, Fairmount Chemical Co., Newark, N.J.; Chromium sesquioxide, 99.86 pct pure, J. T. Baker Chemical Co., Pillipsburg, N.J. Though the materials used were not "hyperpure", the impurities present do not affect the results (lattice parameters, phase boundaries) within the experimental accuracy. EQUIPMENT AND PROCEDURE The detailed procedures and equipment used for this investigation were similar to those described elsewherel' "ith the exception that in this study an induction-heated argon-atmosphere furnace was used. The latter furnace was used to prevent the vaporization of chromium metal in samples in the higher temperature range (above 1200°C). The tungsten crucible was induct ion-heated in a vertical quartz tube filled with argon gas. The quartz tube was 1-1/2 in. in diameter and 10 in. long; it was connected at the top and bottom to water-cooled copper plates. The argon gas of a purity 99.995 pct was further purified by being passed through zirconium metal chips which were maintained at 800°C in a silica tube 1 in. in diameter and 30 in. in length. The furnace was flushed with argon gas for an hour before starting heating; during heating, a slight (3 cm oil) overpressure of argon was maintained in the system. Power was supplied by a 20-kw Ther-Monic Induction Generator. The samples rested on a tungsten-wire basket; the wire basket was connected to a tungsten wire which passed through the tungsten crucible lid, and entered the system on top through a Wilson-type seal. By pulling on the wire, the sample was removed from the crucible and dropped to the water-cooled copper base of the furnace. Because of the presence of argon gas, the cooling of the sample was even more rapid than in the vacuum furnace.' EXPERIMENTAL RESULTS AND DISCUSSION 1) Isothermal Section at 1200°C. The compositions investigated have been numbered within the phase diagram, Fig. 1, and all the pertinent information about the samples can be found in Table I. This table lists the composition of the samples, the phases present in the room-temperature diffraction patterns, the phases detectable in the microstruc-ture, and calculated lattice parameters of the a-zirconium phase. The shapes of the various phase

Jan 1, 1964

By J. W. Martin, L. K. Singhal

Grain boundary M23CB precipitates have been shown to form by a process involving the migration of an austenite grain boundary, and each plate of precipitate is in parallel orientation with one of the austenite grains constituting the boundary. The carbide distribution and morphology appear to be sensitive to grain boundary mis orientation. Some areas of austenite grain bowzdary permit the development of an array of M,C, particles, some of which are in parallel orientation with one grain and some with the other grain constituting the boundary. Massive carbide at grain boundary triple points is also shown to be in parallel orientation with one constituent grain. PREFERENTIAL precipitation during aging of carbides of the type (Fe,Cr)23C6, usually written MZ3C6, in grain boundaries of quenched austenitic stainless steels has been widely recognized. M23C6 has a complex cubic crystal structure' which contains ninety-two metal atoms and twenty-four carbon atoms per unit cell. Less energy is involved in forming grain boundary precipitates than in the formation of intragranular precipitates, and the process is further enhanced by the accelerated diffusion rates in the boundaries and by the probability of segregation of chromium atoms and carbon atoms to the region of the grain boundaries during prior solution heat treatment in order to reduce lattice strain. Early electron micrographic studies2, 3 involving either extraction replica or normal replica techniques established the geometric or dendritic form of the carbide particles, although this approach led to dis- pute as to whether the particles grew within the plane of the boundary or grew into the matrix.4-6 More recent thin-foil studies' have claimed to identify a discontinuous precipitation process involving M23C6 at grain boundaries, and the object of the present work was to attempt to clarify the situation using modern electron micrographic and diffraction techniques. 1) EXPERIMENTAL 1.1) Material. The steel selected for this work had a base composition of 24 pct Ni-25 pct Cr-3 pct Ti and contained about 0.04 pct C. The full analysis if given in Table I. This alloy was in the form of strip which had been hot- and cold-rolled to a thickness of 0.6 mm. 1.2) Heat Treatment. Specimens 4 cm long by 1 cm wide were solution-heat-treated for 3 hr in argon at 1150°C, followed by water-quenching. Specimens were subsequently aged in vacuo at 750°C for periods up to 500 hr. 1.3) Preparation of Electron Microscope Specimens. The heat-treated strips were cut bv spark machining into discs of 3 mm diam and 0.6 mm thickness. he-discs were dished on both sides using an electrolytic jet of 15 pct HCl electrolyte at 80 v. Final electro-polishing of the discs was carried out using 10 pct perchloric acid, 20 pct glycerol, and 70 pct ethanol at 10 v. The current density was kept below 300 ma. cm"2 by cooling the electrolyte to 0" to 5°C. As soon as a small hole appeared, the electropolishing was stopped and the specimen was quickly washed with ethanol.

Jan 1, 1969

By E. Buehler, J. E. Kunzler

High-pu.1-ity molybdenum has been heat treated, melted, and zone refined and the physical and chemical changes that are produced by these processes have been studied by making resistance ratio measurements. Pronounced effects are observed that are associated with recrystalliza-tion at about 1200°C and with melting. Melting alone is found to result in a substantial purification by the evaporation of impurities such as iron. Zone refining is found to be reasonably effective with four passes producing a three-fold decrease in resistance ratio and a minimum ratio of 0.0003. With the aid of low temperature measurenzents, it has been shown that the build-up of a deposit of the material being zone refined on the radio frequency coil used for heating can lead to contamination of the sample. CONSIDERABLE interest in high-purity refractory metals for the study of mechanical properties has developed during recent years. Also the need for highly pure metals in certain fundamental studies, such as electronic band structure, has become quite widely appreciated. Molybdenum can now be produced with sufficiently high purity to make it attractive for such investigations. The most suitable measure of chemical purity of metals used for many of these studies is its resistance ratio, R,.,o,/Ro, During the purification of molybdenum by zone refining and its subsequent evaluation by this technique, a number of informative observations were made. These observations concern the effectiveness of zone refining, the volatilization of impurities at the melting point, and the recrystallization of molybdenum and appear to be pertinent to other refractory metals. Also, the usefulness of low-temperature resistance measurements as an analytical tool for evaluating the presence of chemical impurities and physical defects in metals is again illustrated. Samples of high-purity molybdenum of known mechanical history were heated to various temperatures between 800°c and their melting point. Resistance ratios of the samples were measured after they had been given a specified treatment. The data were used, along with mass spectrographic analysis, as an aid in interpreting the nature of the processes that occurred in conjunction with each treatment. Changes in the concentrations of chemical impurities and physical defects are typical of things that effect the low-temperature resistivity. SAMPLES The starting material was obtained from Westing-house Corp., Bloomfield, N.J. It was in the form of molybdenum rods, usually 1/8 or 3/16 in. in diameter. These had been previously processed from bars, 5/8 in, in diameter, originally reduced from 4 in. diam arc-cast ingots, by hot swaging at about 1300°c. In the final step, the temperature was lowered to about l lOO°C which resulted in the production of elongated grains. Typical grains were about 0.03 mm thick and 0.6 mm long. The molybdenum was quite pure as is indicated by the results of mass spectro-scopic analysis1 given in Column 2 of Table I. Other nongaseous elements not listed in the table were not detected. ZONE REFINING AND THERMAL TREATMENT OF SAMPLES Several sample rods, 8 to 10 in. long, were zone refined or were heat treated at several temperatures. Both types of operations were performed using 3 me-

Jan 1, 1962

By P. Marier, T. R. Ingraham

When cylindrical powder compacts of nickelous oxide (NiO) are heated in an equilibrated stream of SO3, SO,, and 02, in the temperature range 500°to 800°c, tlickelous suljate (NiSO4) is formed as an adherent layer on the oxide. The reaction is diffusion-controlled, with an activation energy of 13 ± 3 kcal per mole. When cylindrical powder compacts of NiSO4 are heated in a stream of dry nitrogen in the temperature range 1000 0to 11500C, NiO is formed at a well-defined interface between the sulfate and oxide. The interjhce migrates into the sulfate at a constant rate at a constant temperature and gas flow. The reaction rate increases with increasing gas flow and decreases with increasing partial pressure of SO3 in the gas stream. Resolution of the partial-pressure data with a Lang-itzliir Adsorption Isothern suggests that about 80 pct of the NiO interface is covered with SO3. The heat of adsovption is about 68 kcal per mole. The activation energy of the decomposition process is 61 ± 3 kcal per mole. MOST of the work reported on the formation and decomposition of nickel sulfate is related to thermodynamics.1-3 No quantitative work has been reported on the decomposition process. The only kinetic work reported on the formation is that by Fletcher and shelef.4-6 whose main purpose was to study the effects of alkali metal sulfate additions on increasing the rate of nickel sulfate formation. They found that, in the absence of an additive, only small amounts of sulfate were formed and the kinetic data were difficult to interpret. However, they suggested that the sulfa-tion of nickel oxide is a diffusion-controlled process for which the activation energy is approximately 17 kcal per mole.6 In this paper, both the formation and decomposition reactions will be examined; and based on the effects of temperature, flow rate, interfacial area, and partial-pressure of sulfur trioxide, mechanisms and activation energies will be suggested for both processes. EXPERIMENTAL Material. The nickel source material used in all experiments was Baker and Adamson Reagent Grade NiSO4. 6H2O, for which the following analysis was supplied by the manufacturer: C1, 0.001 pct; NO3, 0.005 pct; Co, 0.02 pct; Cu, 0.005 pct; Pb, 0.002 pct; Fe, 0.001 pct: insol, 0.005 pct. The anhydrous sulfate was prepared by heating the hydrate at 420°C in a muffle furnace for 5 hr. Nickel oxide was prepared by decomposing the sulfate at 950°C over a period of 10 hr. Method. The technique used for measuring the rates of formation and decomposition was developed earlier in these laboratories.7-8 The method is based on the observation that the kinetic parameters of a reaction can be established in a flow system, with specimens prepared by compacting powder to a uniform pellet shape. The results are identical with those established with solid polycrystalline specimens or single

Jan 1, 1967

By Durell Denysschen, Rafael Abela

The recovery of gold from old mine dumps has been carried out over the last two decades. The gold value and price together with recovery methods, determine whether it is economical to process a dump. Pre-concentration with cyclones and spiral concentrators may offer a method to process dumps considered currently uneconomical to treat.

Jan 1, 2006

By Michael W. Neill, O&apos

The engineering profession generally does not accept vibro-driven piles as bearing piles unless their capacities can be verified by restriking with an impact hammer, which significantly reduces the economic benefits of vibratory driving. In part, the concern for capacity development in piles driven by vibration arises out of observations that vibro-driven piles do not develop capacities equivalent to those driven by impact (e. g., Mosher, 1987). Nonetheless, if capacities are predictable, vibratory installation may be more cost effective than installation by impact, due to savings in time of installation, even if capacities are lower than those of impact-driven piles. Throughout the past few decades, a number of attempts have been made to develop capacity prediction methods for vibro-driven piles, mostly along the same lines as methods for impact-driven piles. That is, (1) totally empirical formulae, (2) power balance / power transfer formulae, and (3) "time domain-nonlinear" (TDN) computational procedures such as the wave equation. Some of the formulae have been based partly on field experience, but the majority have been developed from simple theoretical models with parameters evaluated from laboratory studies. Neither these formulae nor the TDN solutions have been systematically checked (or modified) by recording appropriate field data over a variety of site

Jan 1, 1989

By Y. A. Attia, M. Elzeky

Thiobacillus ferrooxidans bacteria were used in this work to study the effect of bacterial adaptation on the bioleaching of three iron-bearing sulfide minerals, namely, pyrite, chalcopyrite and arsenopyrite. The change in the pH during the bioleaching process was observed and the mechanism of the bacterial action were discussed. It was found that bacterial adaptation prior to bioleaching, enhanced the degree of sulfide leaching by 2-4 folds over that of non-adapted bacteria. A1 so the bacterial activity was enhanced by 2-4.8 folds. The pH of leaching solutions was decreased by the increase in both adaptation period and bioleaching time. It was also concluded that the mechanisms of bioleaching of iron-bearing sulfide minerals involved both the direct and indirect bacterial action simultaneously.

Jan 1, 1989

By P. Wells

"In the past decade, there have been many developments in processing of nickel/copper sulfide ores. Improved pentlandite/pyrrhotite flotation selectivity with the use of new reagents, fine regrinding and Redox measurement (control) has led to increased pyrrhotite rejection and thus higher concentrate grades. Flash flotation has increased overall nickel and associated precious group metal recoveries. Recovery of both fine and coarse particles has been improved through an understanding of flotation cell hydrodynamics. The separation of copper from nickel in such ores has seen a similar level of development. From the late 80s to very recently, the use of flotation columns, the use of pyrrhotite depressing reagents and the improved understanding of the complex mineralogy of chalcopyrite, pentlandite and pyrrhotite have considerably increased copper / nickel separation efficiency. Copper concentrate with more than 30% copper and less than 0.5% nickel grade is now obtainable at 80-85% copper recovery from mill feed compared to 70-75% copper recovery with 30% copper and 1% nickel grade only a few years ago. Improved copper / nickel separation in milling operations has the potential to substantially improve the processing of the resulting concentrates and thus the overall return from the extraction of nickel and copper from sulfide ores.INTRODUCTIONNickel metal by itself or in alloys with other metals and materials makes a significant contribution to modern society. The relatively high price that nickel commands compared to other base metals is a reflection of the fact that, although abundant in the universe, nickel is sparingly distributed in the earth’s crust. There are two types of nickel deposits that are currently being exploited: complex sulfide ores and lateritic oxide ores. Lateritic contain no copper but in sulfide deposits, nickel– bearing minerals, principally pentlandite (Pn, [Ni,Fe]8S9), some millerite (NiS) and violarite ([Ni,Fe]S) are often found in association with copper-bearing minerals, mainly chalcopyrite (Cp, CuFeS2) and cubanite (CuFe2S3). The copper content of such ores can vary considerably from as high as 5-8% (in some Sudbury basin ores) to as low as 0.1% (in ores mined by Western Mining at Mount Keith, Western Australia and by Inco in Thompson, Manitoba). The valuable minerals Pn and Cp are almost invariably found associated with pyrrhotite (Po, Fe7S8) which along with nonsulphide rock has to be rejected to tails in the primary milling stage. The bulk concentrate from the primary stage is then treated to depress Pn and float Cp. A complete Cu/Ni separation at the mill would be highly desirable but this is not possible because of locking between a small fraction of the valuable minerals. As a result, Cu/Ni separation has to be carried out both during milling and during refining of the matte following smelting. At Inco, Jinchuan and in Norilsk, a chalcocite / heazlewoodite separation is made by flotation following slow cooling of the matte. In the present Sudbury Inco operations, Cu/Ni separation has not been conducted at the mill since 1991 and all Cu/Ni separation takes place at the matte processing plant. Because of the rising ratio of Cu to Ni in the ore, this strategy is under review and this paper describes some recent studies of circuits in preparation for possible installation of a copper / nickel separation circuit at Inco’s Clarabelle Mill in the Sudbury area."

Jan 1, 2004

By J. Nakayama

Construction of foundation piles or diaphragm walls through rocky or boulder containing formations has been long-standing difficulty. It has been widely understood that the down-the-hole hammer is the most capable mechanical means but is restricted in drilling diameter by the unavailability of drillhead sufficiently large diameter and the difficulty of disposal of cuttings. A great number of submersible motordrills have been used for the construction of cast-in-place piles and diaphragm walls and the reverse circulation system employed has demonstrated its advantage of the prompt removal of cuttings. The development of multi-head down-the-hole hammer drill combined with reverse circulation system presents a powerful engineering choice for those "hard-to-drill" ground formations. This paper will introduce the features of the system and some actual operation results in the foundation engineering through those hard rocky ground formation in some countries.

Jan 1, 1989

By Shimi Tzobery, John E. Shamma, Samuel Swartz, Gary B. Hemphill

The trapezoidal tapered ring method has made significant progress in recent years for shielded-TBM projects, excavating tunnels with high overburden, strict water tightness criteria, and multiple curve alignments. The selection of compatible tapered rings is critical for successful advancement of the tunnel, assuring efficient installation of rings, as well as prevention of ring damage and excessive leakage. Using experience from the Arrowhead Tunnels Project, this paper describes guidelines for ring selection in tunnel curves, geometric analyses that comply with criteria principals, and provides techniques developed to determine the appropriate relative key position.

Jan 1, 2005

Detailed investigation was carried out on the dephosphorization of a number of phosphorus-rich manganese or samples of India by leaching with dilute sulphuric acid. Various process parameters like concentration of acid, liquid-solid ratio, temperature of leaching, time of leaching, and particle size of the ore were studied in detail for the three samples of manganese ore from central India, and optimum values were worked out on a laboratory scale. Preliminary studies show that certain ores which are not easily amemlible to appreciable dephosphorization by leaching with dilute sulphuric acid can be made amenable by :roasting to 700-900°C before leaching.

Jan 1, 1974

The Coal Resources Survey commenced in 1974 as a search for Huntly Power Station coal, but soon developed into the most detailed regional coal search programme to be instituted in New Zealand. The program was initially conceived as geological in nature, but later included geotechnical, geohydrological, mining assessment, coal use, and environmental considerations in its investigations. The programme never undertook development work but has provided Government and the private sector with a sound basis for identifying development options. The discovery of large-scale coal resources in the Mokau, Waikato, and Taranaki regions and the lignite resources of Otago and Southland are a measure of the Survey's success. The directive by Government to phase out the NZCRS to a large extent coincides with the completion stage of the program. With most of the detailed regional study finished, it now remains to collate the data and publish summary reports at Coalfield and Coal Region level, in order to maximise the use and value of the data collected over the years.

Jan 1, 1987

By William R. Yernberg

A conference on coalbed and coal mine methane was held March 27 and 28, 2000, in Denver, CO. The conference, organized by the Strategic Resource Institute, was attended by leaders in the coal mining and gas energy industry. The conference focused on the recovery of methane from coal beds as an energy resource and the removal and utilization of coal-mine methane (CMM) related to underground coal mining. The two-day conference discussed methane resources around the world, methods of recovery, methane markets, underground coal mining, health and safety issues and environmental issues related to methane. The consensus among the presenters is that the future looks promising for coal bed methane (CBM) and CMM.

Jan 1, 2000

By Mike Muchard

STATNAMIC load testing augmented with embedded instrumentation has been successfully used to obtain structural and geotechnical design information on large diameter spun cast concrete cylinder piles on many large marine construction projects. The paper focuses on one particularly interesting large marine project involving a new bridge to St. George Island, Florida where instrumentation and STATNAMIC load testing was used in conjunction with static load testing on high capacity piles. The information presented includes embedded instrumentation measurements taken during pile fabrication (post-tensioning), during pile driving, during static load testing, and STATNAMIC load testing. As much of this data is the first of its kind on concrete cylinder piles, it is exciting to present the foundation industry with this additional insight as to the behavior of this pile type and the accuracy of the methods used to test them.

Jan 1, 2005