Search Documents

By S. Saito, P. A. Beck

The crystal structure of MoNi3 was determined by means of X-ray diffraction. This structure is isotype with that of ovgered TiCu3. The lattice parameters are: a. = 5.064A, bo = 4.224A, co = 4.448A, and zf 0.157. If the orthorhombic distortion (slight relative to the corresponding orthohexagonal unit cell) is disregarded, the structure may be described in terms of a close-packed ordered atomic layer, stacked in the sequence: abab. The structztres of ordered TiCu3 and TiAl3 are homotectic. The three types of ordered hexagonal phases, iso-structural with TiNi3, MgCd3, and VCo3, are known to occur in AB3 alloys of transition elements of the first, second, ad third long periods. It was noted1 that phases with the TiNi3 structure occur selectively in alloys of Ti-group elements with Ni-group elements. In AB3 alloys of Ti-group and V-group elements with Co-group elements the AuCu3-type structure predominates.' The vCO3 structure, which was determined very recently,' has hexagonal symmetry, but the actual atomic arrangement here, too, is rather closely related to the ordered cubic structure of AuCu3-type. However, an ordered hexagonal close-packed structure of the MgCd3-type occurs in MOCO33 and WCO3.4 Consequently, the question arises as to whether or not the crystal structure of MoNi3 is also of the MgCd3-type. Grube and winkler5 found that MoNi3 has a hexagonal close-packed structure with a = 2.54A and c/a = 1.65. They pointed out that some additional weak diffraction lines could be observed in the powder pattern, which may have been due to an ordered atomic arrangement in this phase. However, no detailed information was obtained by them and the structure was apparently not further investigated by others. The present work was, therefore, undertaken in an attempt to determine in detail the structure of MoNi3, and to investigate the possibility of ordering. EXPERIMENTAL METHODS Alloys used in the present work were arc-melted in a water-cooled copper crucible under helium atmosphere. Electrolytic nickel and molybdenum, both 99.9 pct pure, were used. Chemical analyses were not made, but the melting loss was not higher than 2 pct for any alloy. Ingots were first homogenized at 1200°C for 48hr, quenched, heavily cold worked, and then annealed at 820" or 860°C for 1 week, followed by quenching in cold water. Powder specimens for X-ray work were prepared by crushing the heat-treated solid specimens. In order to remove strains, the powders were reannealed in evacuated scaled fused silica capsules for 6 hr at the same temperature at which the corresponding solid specimens were annealed. X-ray photographs were taken with an asymmetric focussing camera, using unfiltered CrK or CuK radiation. EXPERIMENTAL RESULTS The X-ray diffraction patterns of alloys containing 20.8, 25, and 26.4 at. pct Mo, homogenized at 1200°C, showed the face-centered-cubic structure of the Ni-base a-solid solution. It was revealed, however, by micrographic examination that the 26.4 at. pct Mo alloy contained in addition very small amounts of a second phase, in accordance with the phase diagram.6 On the other hand, the 20.8 at. pct Mo alloy after annealing at 820°C gave the X-ray diffraction pattern of the ordered face-centered-tetragonal MONi4.7 In this pattern several additional weak diffraction lines were also observed, corresponding to the strongest diffraction lines of MoNi3. The alloys containing 25 and 26.4 at. pct Mo after annealing at 820" or 860°C gave X-ray diffraction patterns, as shown in Tables I and 11, corresponding to MoNi3. Each one of the reflections which could be tentatively indexed on the hexagonal close-packed cell of Grube and Winkler,5 with the exception of the basal plane reflections, was split into a doublet, as seen in Table I. Since microscopically the alloy consisted of a single phase, it seemed probable that the lattice of MoNi3 is actually slightly deformed, as compared with the tentative hexagonal unit cell. In addition to these diffraction lines, several weak lines were also present, as shown in Table 11, which could not be indexed at all on the hexagonal close-packed cell considered. Satisfactory indexing of all diffraction lines observed was found to be possible by using an orthorhombic unit cell with ao = 5.064A, ft = 4.224A, and c = 4.448A. These values, whose accuracy is estimated to approximately ± 0.008A, correspond to 95.14A3 for the volume of the unit cell, and to an X-ray density of 9.50 g per cm3. If no attention were paid to the weak reflections listed in Table II, a reduced -unit cell of half the volume (a = 2.532A, b = 4.448A, and c = 4.224A), closely related to the orthohexagonal cell, might be used. The dimensions of the orthohexagonal cell of the same volume as the reduced cell are: a = 2.562A, b = 4.437 A, and c = 4.183A. It may be seen that in the reduced cell the a axis is slightly shorter, while the b and c axes are slightly longer than those corresponding to the orthohexagonal cell of the same volume. This slight orthorhombic distortion is re-

Jan 1, 1960

By C. E. Lundin, M. Hansen, D. J. McPherson

PRIOR work on the Zr-Cu phase diagram by Alli-bone and Sykes,' Pogodin, Shumova, and KUGU cheva,' and Raub and EngeL3 as confined largely to copper-rich alloys. The investigations of Raub and Engel were the most recent and seemingly the most complete of these. Alloys from 0 to 68.3 pct Zr were studied principally by thermal analysis and microscopic examination. These authors reported an inter metallic compound ZrCu, (1116°C melting point) and two eutectics, one at 86.3 pct Cu (977°C mp) and the other at 49 pct Cu (877°C mp). The solubility of zirconium in copper was reported to be less than 0.1 pct at 940°C. The zirconium melting stock consisted of Westing-house "Grade 3" iodide crystal bar (nominally 99.8 pct pure). It was treated by sand blasting and pickling (HF-HNO, solution) to remove the surface film of corrosion product, resulting from grade designation tests. The crystal bar was cold rolled to strip, lightly pickled again, and cut into pieces approximately 1/32 in. thick and 1/4 in. square. These were cleaned in acetone, dried, and stored for charging. The high-purity copper (spectrographic grade) was supplied by the American Smelting and Refining Co. with a nominal purity of 99.99 pct. These copper rods were rolled to strip, cut into squares the same size as the zirconium platelets, cleaned in acetone, dried, and stored. Equipment and Procedures The equipment used for melting and annealing the zirconium binary alloys and for the determination of solidus curves has been described in connection with previous work on the Ti-Si system' and in recent papers in this series describing the studies on eight binary zirconium systems.5-' Techniques employed for preparing and processing the alloys were also similar to those used in the above references. Ingots of 20 g were melted under a protective atmosphere of helium on water-cooled copper blocks in a nonconsumable electrode (tungsten) arc furnace. The ingots were homogenized and cold-worked prior to isothermal annealing to aid in the attainment of equilibrium. The specimens were heat-treated in Vycor bulbs sealed in vacuo or under argon, depending on the temperature of the anneal. Quenching was accomplished by breaking the Vycor bulbs under cold water. Temperature control was within ±3OC of reported temperatures. Thermal analysis was primarily relied on to determine eutectic levels, peritectic levels, and compound melting points. The induction furnace incipient melting technique was also used but did not provide the accuracy obtained by thermal analysis in this system, which involves much lower solidus temperatures than the other zirconium systems. A special technique for the determination of characteristic temperatures was employed in the case of several intermediate phases and their eutectics which displayed very small differences in melting temperatures. Specimens were sealed in Vycor bulbs and annealed at a series of very accurately controlled temperatures. Metallographic examination was then employed to reveal incipient melting. Furnaces and techniques in general were described previously.' The echant used was 20 pct HF plus 20 pct HNO3 in glycerine unless otherwise stated. Results and Discussion The chemical analyses of the majority of alloys prepared for the determination of phase relationships in this system are given in Table I and a brief summary of the equilibrium anneals employed is given in Table 11. In a preliminary program, alloys containing 1, 4, and 7 pct Cu were annealed for three different times at each of the temperatures 700°, 800°, and 900°C. No change in the relative amounts of phases present was detected after 350, 150, and 75 hr at the above temperatures, respectively. The times listed in Table II were accordingly chosen as a result of these preliminary tests. Zirconium-rich alloys containing from 0.1 to 10 pct CU were reduced by cold pressing from 58 to 8 pct, depending upon thk alloy content, homogenized for 7 hr at 900°C, and then reduced 80 to 13 pct by cold rolling, again depending upon copper content. Other alloys were studied in the cast, or cast and annealed conditions. The contracted scope of investigation for this system included the range 0 to 50 atomic pct Cu. This approximate region is shown in Fig. 1. Due to evidence of phase relationships departing considerably from those proposed by Raub and Engel" in the 50 to 100 atomic pct range, the investigation was extended to cover this composition area rather thoroughly also. Fig. 2 is a drawing of the entire diagram. The labeling of some phase fields was omitted in Fig. 2 for the sake of clarity. An expanded view of the zirconium-rich region, with the experimental points necessary for its construction, is given in Fig. 3. The generally accepted value of Vogel and Tonn8 or the allotropic transformation a + 862' ±5OC, was employed in the construction of these diagrams. A careful study revealed that the "Grade 3" crystal bar used in this investigation actually transforms over the approximate range 850" to 870°C, due to impurities. It must be expected that this two-phase field in unalloyed zirconium will cause some departures from binary ideality in the very dilute alloys. Zirconium-rich Alloys: The a + ß transformation temperature is decreased from 862" to about 822°C by increasing amounts of copper. Thus, a eutectoid reaction, fi ß a+ Zr,Cu, occurs at a composition of about 1.6 pct Cu. The eutectoid level was determined to lie between the alloy series annealed at 815" and 830°C. The placement of this eutectoid temperature

Jan 1, 1954

By AIME AIME

IV. THE BOUNDARY BETWEEN STEEL AND IRON. It would be well to decide on a definite carbon-content to serve as a boundary line between ingot-iron and ingot-steel, between puddled-iron and puddled-steel, and between any other varieties of wrought-iron and weld-steel. Two plans have been considered. One is to draw this line at 0.32 per cent. of carbon or its equivalent in other elements, for the reason that this carbon-content appears to correspond to the critical point, 0, in the diagrams of Roberts-Austen and Rooze-boom.8 This has the merit of corresponding to a definite physical boundary. The other plan is to draw the boundary at 0.20 per cent. of carbon, because this is a convenient place to separate the important classes " soft steel " and " half-hard steel," so that if this point was adopted "ingot-iron " would be synonymous with "soft steel," and " ingot-steel " would be the equivalent of the two classes, " half-hard steel " and " hard steel."

Mar 1, 1908

By Fabian Laumen, Sunny Schoone, Felix Leaman, ELISABETH CLAUSEN

The paper evaluates the attenuation behavior of acoustic emission (AE) signals in four different materials used in marine environments. The study aims to identify materials with the highest and lowest AE signal attenuation, providing insights into wave propagation and structural monitoring in deep-sea mining applications.

Dec 1, 2023

By Carlos Mendoza

El presente trabajo describe la optimización del proceso de planta de ánodos en la refinería peruana a través del uso de equipos e instalaciones, sin una necesidad de ampliarlos con los hornos de afino. rueda de modelo o prensa de ánodos. Este proceso utiliza como materia prima las barras de cobre blister, las cuales son enviadas vía ferrocarril desde la fundición de SPCC al norte de la refinería. Luego,este cobre blister es cargado a los hornos junto con los ánodos corroídos, el recirculante de ambas plantas, los desechos de cobre, etc., de acuerdo al programa de flete previo al carguío. Finalmente, se inicia el proceso que comprende: fusión, oxidación, reducción, escorificación y moldeo. De acuerdo a este proceso, la planta de ánodos ha mejorado la calidad física y química de los ánodos e incrementó su producción, efectuando los trabajo en equipos y estabilizando los estándares de seguridad.

Sep 13, 2001

By Yang Song, Li Shaokang, Wang Zhiqiang, Wang Jinjun, Li Guofeng, Su Meixuan

CaCO3, as a component widely existing in natural minerals, is a common impurity. In recent years, triboelectric separation has been applied to the separation of minerals containing CaCO3. However, the CaCO3’ s tribocharging mechanism is still unclear and the charging effect of CaCO3 is not obvious. In order to study the effect of triboelectric charging of CaCO3 particles under different conditions, according to the single particle frictional collision charge-mass ratio formula derived from the condenser model, an experimental platform for particle tribocharging was built in this paper. Then, the formula of charge-to-mass ratio (Q/m) was derived based on the analysis of the particle force. Particle image velocimetry (PIV) was used to record particle motion trajectories to calculate the Q/m of one particle by this formula. In the experiment, the airflow velocity, tribocharge material, and moving distance of the particles were varied to investigate the variation of the particle charge-mass ratio results. The results show that CaCO3 was negatively charged when tribocharging with mental. The particle’s Q/m is positively correlated with the airspeed. When the metal is triboelectrically charged with the insulator, the metal with a smaller work function leads to the insulator particle with a larger Q/m. As the moving distance of the particles increases beyond 230 mm, the particle charge ratio decreases. The particle charge-mass ratio is consistent with the trend of the charge-mass ratio deduced from the capacitance model.

Jun 3, 2023

By M. Fan, Z. Long

"This paper presents some studies on recovering valuable elements from Chinese coal by-products, including coal combustion fly ash, stone coal ash, and coal flotation tailings. Both commercialized technologies and economic potential recovery methods are described in this study. Magnetically stabilized air-dense medium fluidized bed separation, tribo-electrostatic separation, froth flotation, and hydrometallurgical methods are discussed in recovering various valuable elements in Chinese coal by-products from different coalfields. These valuable elements include iron, carbon, aluminum, rare earth elements, lithium, gallium, germanium, uranium, titanium, scandium, silicon, vanadium and phosphorus, etc. The ultimate goal is to fully utilize all valuable elements in coal by-product. Each component within coal by-product should be efficiently segregated to its highest value. INTRODUCTION Coal is mainly composed of energy-producing elements carbon and hydrogen. In addition to these elements, coal usually contains many other valuable elements, including iron, aluminum, silicon, rare earth elements, lithium, gallium, germanium, vanadium, uranium, titanium, scandium, and phosphorus, etc. These coal-associated elements are significantly enriched in coal combustion by-product fly ash because of majority of main components, carbon and hydrogen elements, being removed. Table 1 provides the chemical composition range of the main elements oxides in 12 Chinese fly ash samples collected from coal power plants located in Northeast China, Northwest China, Southwest China, and Southeast China. It can be seen from Table 1 that the major mineral components of different ashes are similar, but the bulk chemistry of different fly ashes may vary widely due to the changes of ratios of the mineral components in different coals. The major mineral components in various Chinese coal combustion fly ash are silicates, iron oxides, and unburned carbon."

Jan 1, 2017

By T. Patching

"COAL MINING at Canmore, Alberta, began in 1886 and continued there until July 1979. A comprehensive review of the Canmore operations is not available, but the following notes have been prepared to accompany references where more complete information about the operations and problems encountered may be found. The coal measures at Canmore occur in the Kootenay formation of Lower Cretaceous age, and at least twelve seams of varying thickness and horizontal extent have been recognized. The coal, of high quality, ranges from semi-anthracite in the lower seams to low-volatile bituminous in the upper seams. The strata of the Canmore area form an asymmetric syncline, the western limb being overturned to vertical by the Palaeozoic strata of the Mount Rundle Range. The eastern limb is more gently sloping, its dip ranging from IO to about 40 degrees. Tectonic movements have created a troubled and complex coal field. The seams were initially not regularly or uniformly deposited, and mountain-building activity folded and faulted the strata and in many places sheared and crushed the original structures of the coal(l,2,3,4,5). The lack of continuity of the seams, and changes in thickness and inclination, made longrange mine planning difficult and necessitated flexible methods of work, and the local disturbances sometimes created problems in roof support and contributed to the occurrence of sudden outbursts of coal and gas. Almost all of the coal was produced from underground operations but a few relatively small V-cut mines were worked along surface outcrops. These have all been filled in and revegetated. The basic method of underground work was by room-and-pillar, but many variations in layout and sequences were employed. Gangways were driven along the strike and pillars were formed by raises or slopes and crosscuts. Pillars were recovered to the extent that ground conditions permitted by splitting or taking 'skips' from the sides of the raises or splits or crosscuts. Because of the variety of conditions that existed in the field a considerable range of cutting, loading and support methods were employed, including hand-loading, slushers and scrapers, duckbills and shaker conveyors, mobile loaders and continuous miners. Except for the coal obtained by continuous miners most of the coal was broken out by blasting when driving narrow working places or by air picks when cutting from a face. In the early years hand loading onto cars or conveyors predominated. A continuous miner was introduced into Canmore in 1959 on a trial basis, and another was subsequently acquired, in order to minimize blasting and hand loading, but problems in operating these machines in inclining seams and difficulties in providing safe roof support for the machines and workers restricted their efficient use. Another major difficulty with the use of continuous miners was the problem of ventilating development headings in the very gassy conditions. In the early 1970s they were replaced by electric and compressed air slushers and scrapers, resulting in a general increase in productivity, roof control, safety, and flexibility of operations(1.6,7,8.9)."

Jan 1, 1985

By Martin Rubenstein

CdS crystals have been grown from a number of metallic solvents such as bismuth, tin, lead, and cadmium. Etching studies have shown that plastic deformation occurs if the crystals are not removed from the solvent prior to the solidification of the solvent, on cooling. The deformed crystals show a umique exciton fluorescence as a function of edge dislocation density. If one grows the CdS in the eutectic alloy of the above four metals (commonly called Wood's metal) the crystals can be removed from the solvent with hot water and no plastic deformation occurs. In this paper, the liquidus solubility measurements of CdS, as a function of temperature, are presented. The data were obtained using a high -temperature filtration technique. CADMIUM-SULFIDE crystals have been grown from a number of metallic solvents1 such as cadmium, bismuth, tin, and lead. Liquidus solubilities of CdS in cadmium,2 bismuth,3 and tin4 have already been measured. Crystals of CdS, in all four metals, have been grown by solution growth: 1) by cooling a saturated solution and 2) by a solution transport method.1'"1 CdS crystals grown in these four solvents have a few characteristics in common: 1) 1.8°K photolumines-cent emission consisted mainly of the radiative recombination of the bound exciton commonly known as I,, 2) slip lines which could easily be seen by the naked eye, and 3) edge dislocation densities in the order of l05 per cu cm.1 It was decided that these slip lines and the high edge dislocation densities were caused by a plastic deformation of the CdS crystals. It was felt that this plastic deformation did not occur during the growth of the crystals nor during the cooling of the solution, but did occur when the solvent which was in contact with the crystals froze. If these assumptions were valid, the slip lines and the high number of dislocations could be reduced or eliminated by removing the crystals from the solvent before the solvent froze. Since crystals of CdS had already been grown separately in such solvents as bismuth, lead, tin, and cadmium, it was felt that crystals could be grown in a eutectic mixture of these four metals. In this work a eutectic (or near eutectic) mixture of bismuth, lead, tin and cadmium in the proportion 50, 26.5, 13.5, and 10 wt pct, respectively, was used to grow CdS crystals. Such a mixture has a melting point of about 70°C and is close in composition to the alloy commonly known as Wood's metals. If the crystals could be grown from this mixture of solvents, and if hot water (>75°C) could be used to separate the crystals of CdS from the metallic solvent, it was hoped that CdS crystals could be grown with little or no plastic deformation which had been ob- served when crystals were grown from these solvents uncombined. CdS crystals were grown from this low melting eutectic mixture of bismuth, lead, tin, and cadmium using the solvent transport method. CdS powder and the appropriate amount of metals were sealed in a quartz tube under a pressure of about 5 X 10-6 torr. This ampule was then placed in a vertical position in a furnace. The temperature was raised to about 900°C. The furnace was designed so that the top of the liquid column within the ampule was between 10° to 40°C higher than the bottom of the liquid column. These temperatures were measured on the outside of the quartz ampule. The ampule was maintained at temperature for 7 to 14 days (depending on the temperature at which transport was taking place) and then the furnace temperature was lowered until the temperature was about 125°C. The ampule was then removed from the furnace, placed in water maintained at about 90°C, and opened in this 90°C environment. The crystals could then be removed from this two-phase liquid (Wood's metal and water) by mechanically picking them out. Alternatively, the crystals could be quantitatively removed by adding an excess of mercury to the mixture of metals, crystals, and hot water. The hot solution of metals and the hot water could be evacuated using a small diameter tube connected to a vacuum. Small amounts of mercury and water could be removed by heating the crystals in vacuum. Crystals prepared using this technique showed no evidence of slip. However, some of these crystals did show edge dislocation densities as high as l04 per cu cm. Some few selected crystals showed no dislocations. Single crystals of CdS were grown as large as 5 by 5 by 0.5 mm. The ampules for the growth of these crystals were 13 mm O.D., 11 mm I.D., 150 mm! LIQUIDUS SOLUBILITY MEASUREMENTS The CdS starting materials was G.E. 118-8-2 powder which was fired in H2S at 1000°C, and then a vapor transport technique5 was applied to produce a "sound" mass of CdS. The Wood's metal was prepared by weighing out bismuth, lead, tin, and cadmium in the proportions of 50, 26.5, 13.5, and 10 wt pct, respectively. The bismuth, cadmium, and lead were from the American Smelting and Refining Co. (ASARCO) and all had purities of 99.999+ pct. The tin was 99.9999 pct spectroscopic grade from the Vulcan Materials Co. The appropriate mixture was placed in a quartz tube, evacuated to a pressure of 5 X 10-6 torr, melted to a liquid, cooled to room temperature under this same vacuum. This ingot was then placed in another quartz tube, evacuated to 5 x l0-6 torr, and sealed off under vacuum. The ampule was then horizontally placed in a furnace. The temperature was raised to 600°C, and over a period of several hours the ampule was vigorously shaken several times. The ampule was then removed from the furnace, and the metallic liquid was

Jan 1, 1970

By J. Clair, H. Mirabel

The determination of the temperature and electrical potential distributicms in the cathodes of aluminum electrolytic cells is difficult. The reascms come from the various nature and the intricate three-dimensional geometry of the materials; besides thermal and electrical phenomena react upon each other. A method of calculation using a computer program applied to a mathematical model, figuring the cathode, is developed. Both of the thermal and electrical phenomena are simultaneously considered. Temperature and electrical potential distributions are finally obtained by successive iterations. Results are compared with measurements on industrial cells. Theoretical and practical applications of these studies are given. Up to the present time the study of the distribution of the temperatures and electric potentials in the electrodes, anode and cathode, of the electrolytic cells used for the production of aluminum was limited to one of the two aspects of the phenomena because of lack of a simultaneous method of calculation. For example, the anode or cathode drop was studied assuming that the temperatures in the iron and carbon are known, a method that obviously is very approximate since iron resistivity, in particular, greatly varies with temperature, which in turn depends on current density. Consequently we tried to find a method of calculation simultaneously taking into account both thermal and electrical phenomena. We proceeded to the study of the cathodes as an initial approach to the problem. Although the cathode and surrounding materials may have varied forms and particularly very heterogeneous characteristics, their structures are simpler than that of the Sijderberg anode and boundary conditions are more easily represented than in the case of anodes even though they are prebaked. The study was in two parts: a) development of a model schematizing the true geometry of a cathode and defining the thermal and electrical boundary conditions, and b) working out a method of calculation of the temperatures and potentials by means of an electronic computer. To facilitate solution of the problem, a model was used initially much simplified in comparison with an actual cathode. This model permitted development of the method of calculation. In a second phase, this model was adjusted to the study of actual cathodes and applied to different types of cells: low- or high-intensity cells, cells set up at ground level or above ground level, cells with cathodes more or less heat-insulated. Simultaneously measurements were made with cells equipped with cathodes of the types studied to compare the values resulting from calculation. The initial model was also used for general studies, in particular for studying the effects of current density in the carbon and iron. The results were confirmed or made precise by the model of the true cathodes. This report successively describes: a) the manner in which the model representing a cathode was worked out, with the simplifications and/or the hypotheses used, b) the method of solution of the problem by means of the electronic computer, and c) an example, stating the extent to which the results obtained may be realistic. Further the possibilities offered by such a study are examined. 1) CATHODE REPRESENTATION The purpose of this phase is to represent the cathode in the form of a so-called "mathematical model", that is with a simplified geometrical configuration, in order to meet the subsequent calculation requirements, while keeping to the true facts as closely as possible. This model further includes the thermal and electric conductivities with regard to temperature for the varied materials composing the cathode, as well as the thermal and electrical conditions at the model boundaries. 1.1) Guiding Principles. For calculating the temperatures and potentials the model is divided by trior-thogonal planes into a network of small elementary parallelepipeds. At the summit of these parallelepipeds' so-called mesh points, the temperatures and potentials are computed. The number of mesh points is of course limited by the capabilities of the computer, since 1) the number of equations to be solved depends on the number of mesh points selected, and 2) the amount of time spent by the computer considerably increases with increasing this number. These conditions call for the following requirements as concerns the model: a) Dimensional requirements: the calculation will be all the more accurate as the network is more closely meshed. Since the number of mesh points is limited in practice, it is necessary to restrict the dimensions of the model. b) Geometrical requirements: so as to make things easier in working out the network, the model must be given a simple geometry. In particular, it will be convenient to have the cathode so constituted that the surfaces limiting the cathode and the surfaces within the cathodes separating the different materials consist of triorthogonal planes. 1.2) Schematization of the Cathodes. After the tech-

Jan 1, 1968

By V. B. Kurfman

Grain refinement of Mg-Al melts by carbonaceous additions has been attributed to nucleation by aluminum carbide. The effects of process and alloy variables are interpreted and predicted in terms of the dispersion and chemistry of this phase. The grain coarsening action of Be, Zr, Ti, R.E., chlorination, temperature extremes, and prolonged holding times is described. Measures necessary to insure an adequate dispersion of the catalyst are discussed. CARBON inoculation treatments have become fairly well known and used for grain refinement of magnesium alloys containing Al. Although there is general agreement that a nucleation process occurs, the process is not understood and the inoculants are used in a rather empirical fashion. The treatment is applied to the class of alloys containing 3 to 10 pct Al, i.e., AZ31A to AM100A. Typical methods involve melting, alloying, and adjusting the temperature to 1400° to 1450°F. Then 0.01 to 0.5 pct C as CaC2, C6C16, or lampblack is added by any convenient means, and the melt poured within 10 to 30 min. Investigators generally have been impressed by an assumed similarity of this refinement process to superheat grain refinement, which depends on heating approximately the same alloys to a temperature in the range of 1550" to 1650°F, then pouring promptly after the melt is cooled to the pouring temperature. Various predictions have been made that carbon refinement would replace superheating in commercial practice due to reduced process costs, but this replacement has not fully taken place because of production difficulties and conflicting observations. Davis, Eastwood, and DeHaven1 agree with Nelson2 and wood3 in suggesting that an excess of inoculant may be harmful. Wood however says that overtreat-ment is not a problem in production use of hexa-chlorobenzene inoculation, and Hultgren and Mitchell4 claim no evidence of harm from excess additions. Various grain coarsening reactions are known to occur, including the possibility of overtreatment mentioned above. Trace amounts of Be,2 Zr, and Ti may prevent refinement by either a carbon treatment or a superheat. Occasionally treatment with cl25 may cause coarsening, although the Battelle refinement process' uses a CC14-C12 blend. Grain coarsening also tends to occur on holding at temperatures below 1350°to 1400°F, especially after a superheat treatment, and for this reason Nelson2 stresses the desirability of a refinement method useful at lower temperatures for open pot melting practice. Since a carbon treatment can be made to work at temperatures below 1400°F, it seems desirable to investigate the mechanism of the refinement and the mechanisms of the coarsening reactions in order to establish control conditions for use in commercial production. The identity of the nucleating phase must first be established and then the factors affecting its chemistry and physical dispersion must be determined. THE IDENTITY OF THE NUCLEATING PHASE Davis, Eastwood, and DeHaven suggested that the nucleating phase in this system is Al4c3,1 but Mahoney, Tarr, and LeGrand8 disagree, largely because they found no evidence of the compound in alloys after carbon treatment and because there is no indication that aluminum carbide should be unstable over the temperature range used in the superheat treatment. This latter objection is based on the assumption that both the carbon treatment and the superheat treatment introduce the same nuclei. Electron diffraction studies have been made to identify the nucleating phase. Samples of grain refined A292 have been selectively etched SO that clean surfaces are obtained and so that secondary phases are in relief. Electron diffraction patterns from these surfaces have established that the carbon treatment of A292 introduces into the metal a large number of small, plate-like particles with a structure very similar to Al4C3. In most cases, the plate-like nature of the particles prevented positive identification but in the cases where the identification could be made the particles proved to be AIN A14C3. However, enough variation in lattice constants was observed so that all compositions from pure A14C3 to the 50:50 solid solution A1N.Al4C3 were probably present.14 In A14C3 and especially AlN.Al4C3 the A1 atoms occur in layers within which they have the same hexagonal symmetry and spacing as the Mg atoms in a single basal plane of a magnesium crystal. The solid solution spacing lies between the 3.16 of AIN and the 3.3? for Al4C3, in satisfactory agree-

Jan 1, 1962

By J. E. Strassner

Oilfield emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases. Adding inorganic acids and bases radically changes the physical properties of these films and their emulsion-stabilizing properties. Interfacial films show one of three different physical characteristics when retracted in pendent drop tests. These compressed films have rigid, soap-type or minimum film properties depending on the quantity of asphaltenes and resins in the crude oil and on the pH and composition of the brine. There exists for each crude oil-brine system an optimum pH range over which the adsorbed film exhibits minimum contracted filtn properties. In this range, intmfacial tension is high — frequently near its maximum value — indicating the absence of highly surface-active specier; crude oil-brine emulsions generally show minimum stability; and surfactant requirements for breaking these emulsions are significantly reduced — sometimes no surfactant is needed. About two-thirds of the world's crude oil is produced as emulsions that must be treated (demulsified) to be marketed.' Approximately three-fourths of all domestic crude oil produced must be treated. The percentage of crude requiring treatment increases as fields become older and more water is produced. Demulsification most frequently is attained through use of surfactants, heat and electric treaters. It is estimated that over 75 percent of all oilfield emulsions are broken by chemicals generally containing alkylene oxide condensates. Although acids and bases are known to affect emulsion stability:-' they rarely are used in the oil field except in batch treatment of the most severe emulsions. Nevertheless, pH adjustment by using acids or bases in demulsification has some advantages over other methods. Mainly, it is cheaper. Acids and bases frequently are cheaper to use than surfactants, or can appreciably reduce the amount of surfactant required for demulsification. Secondary advantages are that less oil is lost by emulsi-fication into the aqueous phase, and that less corrosion is encountered when the optimum pH is basic. Limitations to the use of pH include (1) use in brines containing high concentrations of reactive ions, (2) closer supervision for pH control than is required for surfactants and (3) need for corrosion protection when the optimum pH is sufficiently acidic. These factors indicate that the economics of pH con trol in demulsification will be maximized when relatively large treating facilities are needed, when relatively large surfactant concentrations are required to break an emulsion, when a relatively low concentration of the aqueous phase is emulsified in the oil and when the emulsified aqueous phase contains relatively low concentrations of reactive ions. Because there are no broad guide lines for using pH control in breaking oillield emulsions (and because the limited guides available are highly specific and frequently contradictory), this paper will attempt to clarify the principles involved in using acids and bases to break emulsions. These principles also should be useful in refinery separations and in other oilfield applications where stable or unstable petroleum emulsions are involved. Principles of Emulsion Stability Oilfield emulsions generally occur as water droplets dispersed in oil (w/o) and occasionally as oil droplets in water (o/w). These emulsion droplets are usually in the 0.1- to 10-micron range. However, more coarsely dispersed water droplets frequently are present in the emulsion. Pure hydrocarbons and water will not form stable emulsii except in extreme dilutions where the large distance brtween droplets inhibits coalescence. An emulsion breaks because interfacial tension acts to minimize the surface area of the dispersed drops by coalescence. However, emulsions can be stablized for long periods of time by the presence of a third phase that adsorbs at the oil-water interface and inhibits coalescence of the dispersed phase."' Emulsions generally are stabilized by (1) repulsive charges on the surfaces of the dispersed phase and (2) adsorbed films that, being preferentially wetted by the continuous phase, act as a physical barrier to inhibit contact between the dispersed droplets. Both these factors generally are important in stabilizing and in breaking o/w emulsions. However, repulsive charges are less effective in stabilizing w/o emulsions which generally are stabilized by adsorbed films.V or this reason the nature and importance of these films at oil-water interfaces were examined closely; as will be shown, pH changes were found to affect the films significantly, and this work led to laboratory tests of pH- adjustment in emulsion breaking. This paper will present evidence to show that emulsions are stabilized primarily by films that form around droplets

Jan 1, 1969

By G. I. Mathieu

"An experimental study was carried out to evaluate the performance of column flotation versus conventional flotation for the recovery of molybdenite from a Newfoundland ore. The objective was to verify the claims made by the inventors of the flotation column, Messrs. Pierre Boutin and Remi Tremblay, that their apparatus reduces the entrainment of fine gangue and other mineral impurities in the froth product. The research included a factorially designed series of tests to determine satisfactory operating conditions of the column. These provided a basis for comparative flotation tests with column and Denver cells. In the course of the work, the action of a few depressants was studied. Results indicated greater selectivity in the column and reduced reagent consumption."

Jan 1, 1972

By Saskia Duyvesteyn

Ion flotation is a technique applicable to the removal of metal ions from dilute solutions, using ionic surfactants.- While there are a number of physical and chemical parameters that influence the ion flotation process, this paper focuses on two of the important chemical ones, namely frother concentration and ionic strength. The effect of several frothers, including ethanol, iso-propanol and MIBC at concentrations ranging from 0% to 0.4%, was studied for the model Cd-dodecylsulfate and Cu-dodecylsulfate systems. The ionic strength, as well as the effect of monovalent and multivalent counter ions, was also studied in the range of 1@3 - 1 M, at constant pH. The results are discussed in terms of applicability to a range of effluents from minerals and materials processing operations.

Jan 1, 1994

By F. Keller, A. H. Geisler

Some of the important changes that take place in the structure of aluminum alloys are largely submicroscopic in character. This is especially true of the changes that accompany age-hardening and recrystallization. Although improved metallographic practices have been helpful in indicating some of these changes indirectly, results are limited by the resolving power of optical microscope lenses. The electron microscope, however, provides a new and important means for investigating the fine structure of metals in a range not possible heretofore. It is anticipated that this microscope will yield new and useful information to metallurgists when suitable techniques are developed to utilize its very high resolving power. Several unique methods have been devised to permit the examination of the structure of opaque samples by the electron microscope. These are all based on the principle of producing a very thin film that represents the prepared surface of the opaque metal sample, which can be examined in the transmission microscope; however, the available methods fall into three categories, depending on the manner in which the film is obtained. With the oxide-film method developed by Mahl3-17 a very thin surface layer of the metallographic sample is converted into oxide by a thermal, chemical or anodic treatment. After removal from the metal sample by one of the special techniques described by Evans,19 this oxide film is examined in the electron microscope, and is found to portray the structure of the original metal surface. Films formed on aluminum,8,17 nickel,7 iron 3,8,9 and a nickel-beryllium alloy" by heating; films formed on iron 8.9 by chemical action; and films formed on aluminum3-16 by anodic oxidation, have been examined. The other two are more recent methods developed principally in this country; they consist in making the thin film in the form of a mold or replica of the surface contour of an etched sample. With the negative replica method the thin film is made directly on the sample; with the positive replica method it is made on a negative reproduction of the sample. With both methods, variations in the contour of the metal sample, caused mainly by etching, produce variations in the thickness of the surface replica. Because of the direct dependence of the amount of scattering of the illuminating electrons upon the thickness of the film penetrated, only the variations in thickness of the replica are responsible for tones in the electron image. Negative replicas are made by forming a thin film of some suitable material directly on the polished and etched metal sample, and derive their name from the fact that after removal from the sample they have the high and low points in the sample reversed, as shown in Fig. I. Nega-

Jan 1, 1944

FRank FirmstoNe, Easton, Pa.: The effect of lead on brass seems to have been recognized by Berthier, and the facts published by him as early as 1818 (Ann. des Mines, 1st ser., iii., 1818, p. 347 et seq.). He there says expressly that copper containing lead makes " dry " (see) brass, and that, for the same reason, blast-furnace

Jan 1, 1898

The process design of a metallurgical plant follows logical steps, one built on another, to define the circuit requirements. The methodology used and documentation produced is the same for a pre-feasibility study, feasibility study or a complete design, regardless of the process complexity or the commodity. The only difference is the amount of detail developed at each stage. SRK Consulting, an independent, international consulting practice that provides focused advice and solutions to clients, mainly from earth and water resource industries, has consulted on many mining projects around the world. The company was formed in 1974 and now employs more than 1,600 professionals in more than 50 offices on six continents. According to SRK experts, the first element in plant design is collecting metallurgical testwork or operating data from an existing plant. The testwork identifies the process, the metallurgical recoveries and product qualities and establishes the process parameters for economic recovery of the commodity. Test samples must represent both the whole orebody and the feed over the life of the mine, showing the mineral?s variability. With this data available, the process design can be developed.

May 1, 2013

By S. Terry, W. Callender, R. J. Cornelius

When a dry ball-mill grinding circuit was in- stalled at the pellet plant of Hamersley Iron Pty. Ltd., it was something of a pioneering venture, since this was one of the first instances where such a circuit had been applied to iron ore on a major scale. The Hamersley pellet plant is located in Dampier on the coast of Western Australia. The feed for it consists of -8mm fines produced as a screened product at the Mt. Tom Price mine 186 miles inland from Dampier. It was these fines that encouraged the choice of a dry grinding facility for the plant. At the outset, tests had shown that the fines could not be filtered satisfactorily with a wet grinding system. At the pelletizing plant, the fines are stockpiled, reclaimed, dry ground in ball mills, formed into pellets on balling discs, hardened on an indurating line, and stockpiled for shipment overseas. These operations are shown in Fig. 1.

Jan 7, 1969

By P. G. Shewmon, H. E. Collins

We have studied the effect of adsorbed sulfur on the surface self-diffusion of copper using eight diflerent surface orientations and the grain boundary grooving method. The eight orientations studied were the four lying near the low-index surfaces—(loo), (Ill), and two directions in the (110)-plus four higher-index surfaces. Surface-diffusion measurements were made over a range of HZS concentrations (in Hz) from 3 to 1500 ppm between 830°and 1050°C. The results can be divided into two groups—Group 1 contains the two (110) surfaces while Group 2 contains the remaining six surfaces. In Group 1, increasing the temperature increases the effect of Hz S on DS for the Hz S range 5700 ppvn. Qs and Do increase with increasing H2S concentration in this Hz S range. Beyond this range, increasing the temperature decreases this effect on D,; also Q, and Do decrease. In Group 2, increasing the telnperature decreases the effect of H2 S on D, for the H2S range studied, and Qs and Do decrease with increasing Hz S concentration. In any study of surface phenomena, there invariably arises the question of the possible presence of and effect of adsorbed impurities. Such questions are well-founded since the presence of adsorbed atoms can sometimes produce marked changes in the kinetics of surface-energy-driven processes. In the last few years, values of the surface self-diffusion coefficient, D,, have been determined on a variety of metals by studying the decay of scratches or the growth of grain boundary grooves.L~3-L0~L3 Yet there has been relatively little work done in which the concentration of an adsorbed impurity was systematically varied and the effects observed. Work of this sort would provide some basis in fact for the assertions often made about the ro1.e of adsorbed impurities in the differences between the results of different workers in different atmospheres and on different metals. It also is relevant to those cases in which surface monolayers produce profound effects in commercially important processes. The most marked example of such effects is the ability of nickel or palladium to increase the sintering rate of tungsten by many orders of magnitude.' The aim of this work was to study the effect of sulfur partial pressures on the surface self-diffusion of copper. It was felt that this in conjunction with a study of the degree of adsorption and type of active sites involvedL8 would provide a wide range of data for one system and hopefully lead to some insight into the mechanism by which sulfur adsorption influences copper diffusion. The main reasons for choosing the Cu-S system were, first, faceting was reported not to accompany the adsorption of sulfur. This is required if our experimental technique is to work. Second, Oudar has determined a high temperature adsorption isotherm for this system, an event which puts the Cu-S system almost in a class by itself.I4 EXPERIMENTAL PROCEDURE Initially, we considered studying the effect of an adsorbed impurity on surface self-diffusion of copper using isolated (or single) scratch smoothing as the technique and oxygen as the impurity. Copper was chosen as the material because the effects of orientation and anisotropy of the surface self-diffusion coefficient, D,, of copper in a dry hydrogen atmosphere had been studied extensively by Gjostein' and by Shewmon and ~hoi.~,~ The isolated scratch technique was chosen because both the effects of surface orientation and anisotropy of D, in a given surface could be easily studied with this method.~ Oxygen was tried as the impurity because Robertson and Shewmon""~ had studied its adsorption on copper at 1000°C over the range of oxygen partial pressures of 10"22 to 10-l3 atm. After several preliminary runs, it became evident that neither the scratch technique nor the impurity oxygen would be satisfactory for this work. Scratching deforms an annealed surface so that the region near the scratches recrystallizes, thereby disrupting the scratch profiles. One can avoid this by deforming the specimen sufficiently before scratching to give complete recrystallization on subsequent heating.4 However, as a result of Gjostein's success in scratching and annealing undeformed gold single crystals without local recrystallization,13 we attempted something similar with copper single crystals using a 0.7-mil diamond phonograph needle mounted in a Tukon hardness tester. All specimens recrystallized upon being annealed. Also, some copper specimens were sent to Gjostein to be scratched using his technique. The results were the same. As a result, the scratch technique was dropped in favor of the grooving of symmetric grain boundaries. Preliminary work using oxygen showed that faceting began to occur before oxygen adsorption had any measurable effect on D, at 938°C (at Pbo/P, = 0.12). Since heavy faceting would interfere with the measurement, we decided to use a sulfur-containing atmosphere (H2S/H2). Work by Oudar and Benard' and Robertson" showed that sulfur absorbed on copper and that faceting was not observed.

Jan 1, 1967

By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970