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By C. S. Sivaramakrishnan, Manjit Singh, Rajendra Kumar

Regarding liquid nzetals structurally as a suspm-sion of clusters , having derivated solid-state coordination, in truly liquid atoms, the recently developed Kuvlar-Samarin technique of centrifuging- in liquid state enabled the determination of the cluster sizes inAl-Cu mid Pb-Sn systems. It is shown that the colutne fraction of the clusters does not exceed 9 pct and the energy of their formation in Al-Cu is about 5.5 kcal per g-atom and in Pb-Sn eutectic alloys about 25 kcal per y-atoni. STRUCTURAL investigations of liquid state have principally followed the following three courses: i) studies with X-ray, electron, or neutron diffraction; these investigations have shown that there is a certain amount of regularity in the structure of liquid metals which can be defined by a coordination number and that the structure is a derived function of that in the solid state; ii) thermodynamical investigations which are based on the concept of ideal behavior; these describe the liquid state in terms of free-energy values and other thermodynamic functions; although these investigations are of help in the study of the general effects of alloying, they do not provide any structural insight into the precise atomic distribution in liquid state; iii) measurements of surface tension and viscosity; although it is natural to expect that the viscosity is related to the structure in liquid state, these investigations have so far only provided information which can be used by the foundry technologists and has been little utilized in formulating models of the structure of liquid state. As it happens, investigators in the three groups have worked almost independently of each other and there is practically no structural correlation between the results of one group with those of another. The purpose of the present paper is to indicate that the experimentally measured parameters of these three groups of research are closely related to the structure in the liquid state. STRUCTURE OF LIQUID METALS Although atomic distribution in solid and gaseous states is rigorously known, that of the liquid state is only appreciated on the fringes. There is no universal model of atomic distribution in liquid state, but two diverse models are at present hotly contested. The first, largely expounded by ~ildebrand,' regards the liquids as condensed gas since many of their properties and much of their behavior can be adequately described by regarding them as fluids. The second mode12j3 considers that some form of near-solid as- sociation of large number of atoms exists in the liquid state. On the other hand, ~ernal' was able to predict rather precisely the radial distribution functions in liquids on the basis of statistical geometric approach which considered that liquids are "homogeneous, coherent, and essentially irregular assemblage of molecules containing no crystalline regions or holes large enough to admit another molecule". He introduced the concept of pseudonuclei in the otherwise random structure as aggregates of closely packed tetrahedra which gradually merge into irregularity and continually replace each other. To what extent the pseudonuclei can be regarded as regions of near-solid association is indefinite but Bernal suggested that the concept of pseudonuclei can be compromised with the latter model if the near-solid associations are regarded as extremely dense and not necessarily crystalline. The difficulty in projecting the structure of liquid metals arises because they exhibit duplicity of character as some of their properties are closer to those of crystalline solids and others to fluids. There is an increasing tendency to discuss the structure of liquid metals in terms of the second concept according to which the structure of liquid metals may be conceived as consisting of i) clusters of atoms where the aggregation is a close derivative of that in the crystalline state, ii) individual atoms which behave like true liquids in respect to degrees of freedom and iii) excess number of vacancies. It is noteworthy that the introduction of only 5 pct vacancies is sufficient to transform crystalline matter into the liquid state. At any instant of time thermodynamic equilibrium exists between i, ii, and iii, but the relative proportion of the clusters and random atoms is not known. That this is so can be appreciated by the fact that, when liquid metal is rapidly cooled, liquid state vacancies may condense in the form of dislocation loops and vacancies in excess of their equilibrium number in solid state. These dislocation loops have been observed in thin foils of aluminum prepared from rapid cooled aluminum. As temperature increases above melting point the number and volume fraction of clusters decrease but those of vacancies and random atoms increase. Clusters are transient in nature. In pure metals the cluster is an aggregation of the metal itself. In alloys, however, the nature of the cluster largely depends on the interaction between solvent and solute atoms. If the interaction between unlike atoms is greater than between like atoms: the clusters are then aggregates of unlike atoms. Examples of this kind of system are A1-Cu, Mg-Pb, and so forth, i.e., systems which exhibit negative departures from the Raoult's law. In systems where the interaction between unlike atoms is smaller than be-

Jan 1, 1968

By Joseph R. Stephens

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

Jan 1, 1969

By Gordon E. Agar, David M. Hopstock

This paper describes the procedures and results of a series of experiments conducted to determine the depressing effect of sodium, calcium and magnesium ions on the amine flotation of quartz. It also presents an analysis of the experimental results by the electrical double layer theory. The flotation of quartz with primary amines has been practiced on a large scale in the phosphate industry for many years. Some glass sand —and recently iron ore — has also been treated by this flotation technique. These applications have been highly successful and demonstrate that a complete mastery of all the details of an operation is not needed to achieve an economic success. There are times, though, when it becomes important to recognize, both qualitatively and quantitatively, the effects of some previously ignored variables. The effects of cations on the amine flotation process, particularly those ions that contribute to water hardness and abound in sea water, are a case in point. In conjunction with the development of a cationic flotation reagent for separating quartz from apatite, it became necessary to quantify the influence of calcium and magnesium on the separation. In order to strengthen and broaden current understanding of the flotation process, the results were interpreted by means of the electrical double layer theory. THEORETICAL BACKGROUND Assume that, given the same equipment, procedure, and time, the recovery of quartz by amine flotation is a function of only the adsorption density of aminium ions in the Stern layer, i.e., that for any given adsorption density there exists only one recovery percentage. By the Stern-Grahame treatment of the electrical double layer,'-' for any ionic species in a solution in equilibrium with quartz,

Jan 1, 1969

By R. T. Pepper

DURING an investigation into the effect of heat-treatment on the creep properties of the magnesium alloy ZW1, (1 pct Zn, 0.6 pct Zr), the previously published methods of final polishing were found to be unsatisfactory. A new diamond-polishing technique has been developed to facilitate the study of fine precipitates in this and other magnesium alloys, and is described in this note. The sectioning and coarse grinding techniques are those of Fox and Hall,' and Hess and Cieorge.' Pre- liminary mechanical polishing is done with 6-µ, and 1-µ( grades of diamond compound on 'Microcloth' using a lubricant of 'Hyprez' oil. When the conventional technique is used with a 1/4- µ diamond wheel for the final polishing of magnesium alloys, scratching is likely to result from the abrasive action of the 'Microcloth' nap on the soft metal surface. This problem has been overcome by the use of a cream on the wheel in order to separate the specimen surface from the polishing cloth. To prepare this cream, a solution of 6-ml tri-ethanolamine in 75-ml water is stirred into 12.5 g stearic acid at a constant temperature of 80° to 90°C. The cream is allowed to cool, and is then 'whipped' to a smooth consistency with 100-ml 'Hyprez' oil. Before polishing, the diamond loaded 'Microcloth' is moistened with a few drops of 'Hyprez' oil, then a small amount of cream is worked into the nap. For the best results a wheel speed of 500 rpm should be used for polishing, and the specimen should be held by hand with a light pressure while being rotated in the opposite direction to the wheel. After polishing it is necessary to swab the specimen thoroughly in methylated spirits to remove residual cream and oil from the surface in order to avoid uneven etching and drying stains. Fig. 1 shows the surface finish obtained on a specimen by polishing on a 1/4- ° diamond wheel using the cream, and Figs. 2 and 3 the precipitate observed in ZW1 after polishing, and etching for two seconds in nitric acid 15 pct in ethylene glycol. This new diamond-polishing technique has made a valuable contribution to the programme of metal-lographic research on ZW1 and has become a routine laboratory practice for other low alloy content magnesium alloys.

Jan 1, 1961

By A. A. Berk

LAGGING technology and the slow spread of information have been the chief obstacles to widespread participation in minimizing the industrial pollution load. These obstacles can be conquered by fact finding and applied research. There are three aspects to the problem of water-borne mineral waste: to minimize the amount being thrown away, to select a predisposal treatment, and to use the products or dispose of them. It is often possible to minimize the waste by making very minor changes in the process that produces it. For example, a manufacturer of automobile bumpers greatly reduced the dragout 'from a plating bath by modifying the design and position of two boltholes.' A plater of automobile hubcaps installed a drainage bar and decreased the loss of chrome-plating solution to the rinse water by about 80 pct.' The mill at a western mine found it possible to discard 60 to 70 pct of an ore with minimum treatment," so that the processing effort could be concentrated on a high-graded slime, with significant reduction in costs and improvement in recovery. The possibilities for waste reduction through process changes are limited only by the imagination. A recent patent points out the advantages of using No. 1 fuel oil instead of water in wet-process cement making;& the fuel oil presumably has better properties than water for this purpose and is said to be almost com'pletely recovered or utilized, so that there is no waterborne waste. Recycling to reduce wastes and improve process economy is very well illustrated in vanadium and uranium recoveries from relatively low grade ore. Ores containing 6 pct calcium carbonate were found to give poor vanadium recovery by the salt-roasting process because the vanadium was converted to water-insoluble calcium vanadate. Following the salt-roasting process, sulfuric acid was used to leach the uranium. Enough calcium sulfate was formed

Jan 1, 1958

By Garth M. Crosby, F. McIntosh Galbraith, Bronson Stringham

THE Hercules mine is located in the northeastern section of the Coeur d'Alene district, approximately 1 1/2 miles north of the town of Burke, Idaho. Surface indications of the ore deposit were first discovered in 1886, but regular mine production was not started until 1902 and was continuous until April 1925, when the known ore had been extracted. Incomplete records show that from 1912 until operations were suspended the mine produced 2 1/2 million tons of ore containing 9.4 pct lead and 7.7 oz of silver per ton, together with an estimated 2 pct zinc, 0.3 pct copper, and 20 pct iron. This operation was the first in. a series of mining enterprises culminating in October 1947 with the consolidation of Day Mines, Inc. In the same year it was decided to unwater the levels below the collar of the Hercules shaft in the hope of finding some indication of a recurrence of ore. The unwatering operation has been described in a. previous paper.' The initial exploration, following recapture of the workings, showed sufficient promise to warrant a detailed study of the mineralogy with modern techniques. The general geo1ogy of the Coeur d'Alene district, including a detailed description of the rock types encountered, has been comprehensively treated by Ransome and Calkins' in their classic paper, and only local background description, therefore, is felt to be appropriate here. The Hercules deposit transects a portion of the trough of a broad south-trending synclinorium which has been greatly complicated by faulting. More locally, it lies within a block of ground bounded on the east; by the O'Neil Gulch fault, a steep north-south overthrust of considerable magnitude, and on the west by a monzonite stock, the outcrop of which is 1/2 mile or more wide and 5 miles long. The country rock is composed of thin to medium-bedded argillites and argillaceous quartz-ites of the Prichard and Burke formations, the oldest members of the Pre-cambrian Belt Series of sediments in the area, believed to be of Algonkian age. The contact between them is a conformable gradation. The argillite is colored gray to tannish-gray and is fine-grained, compact, and generally massive in structure. Under the microscope the unaltered argillite is seen to be composed principally of anhedral quartz and a few feldspar grains which were at one time presumably partly rounded sand grains, but as a result of recrystallization and cementation by silica, the interstices are now almost obliterated and quartz grains show crenulate boundaries. The sizes of these crystals vary from 0.5 mm down to 0.1 mm in greatest dimension. In all specimens sericite comprises 10 to 20 pct of the rock and is present abundantly between most of the grains as flakes or shreds which vary considerably in size. Sometimes they form a fine felt-like mat or aggregate, and sometimes flakes are seen which appear to be good muscovite. In some specimens, separated rhombic-shaped carbonate grains are abundant, and in some instances these have been changed to sericite. Mining operations to date have explored the Hercules vein to a maximum vertical depth of 3600 ft below its outcrop, and along a maximum strike-length of 3600 ft on certain of the lower mine levels. The main orebody is irregular in outline, extending over a variable strike-length of 400 to 1500 ft; and it is intersected by a strong transverse fault that has been traced from the surface to the bottom level. This has been named the Hercules fault, and apart from the vein itself, it is the most prominent structural feature in the mine. There is good evidence that it existed prior to the introduction of ore solutions and may have influenced ore deposition, but it was also the locus of important post-ore displacement and shows a progressive right-handed horizontal component reaching 200 ft on the deeper levels. Its vertical component is not definitely known but may be considerably greater. The fault strikes 20° N to 50° E and dips westerly at angles of 70" to 45", flattening in dip where it crosses the original orebody from east to west between 1000 and 1600 ft below the surface. At about 3000 ft in depth the Hercules fault is joined by a vertical fault of similar strike, and the major post-ore dis-placement below their junction is taken up along this vertical branch of the structure, now called the Mercury fault. Recent work has been concentrated in this vicinity. Another structural feature of special geologic interest, though of little economic importance, is the occurrence of a porphyritic dike in this area. This lies a short distance above the Hercules fault, essentially parallel to it, and is 5 to 15 ft in thickness. It appears at first glance to cut the mineralization, suggesting push-apart relationship, but small stringers of the vein minerals have been observed to penetrate the dike for a matter of inches at several points. The dike is thought to be related to the monzonite intrusion. A vertical longitudinal projection of the mine is shown in Fig. 1, which illustrates most of the features discussed above. The Hercules vein was deposited along the course of a strong, persistent shear zone that now appears as a braided network of gouge seams running through more or less crushed and shattered country rock. It strikes 70° N to 80° W and dips southerly at an average of 75". Barren parts of the structure vary in width from less than 1 ft to more than 15 ft. The width of mineralized segments may be double that. Although the evidence is not conclusive, pre-mineral, normal movement along the zone may be 1000 or 1500 ft. The horizontal component is unknown. Post-ore movement appears to have been

Jan 1, 1954

By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956

By R. S. Dean

The careful work of Gross and Zimmerleyl has established the fact that the energy actually used in grinding is proportional to the new surface produced. This confirmation of Rittinger's law was made by crushing quartz in a frictionless drop-weight machine and determining the surface of the quartz by its rate of solution in hydrofluoric acid. The details of this procedure have been described adequately elsewhere and need not be repeated here. The resultant data furnish the only available basis for comparing accurately the efficiency of grinding machines. This method is so cumbersome experimentally that it has been little used. As an alternative all sorts of approximations have been proposed. The best of these is complete size analysis by sieving and elutria-tion. Such procedure is very lengthy and difficult to carry out accurately. Furthermore, any sizing method becomes very inaccurate for determining surface with very fine sizes where the ratio of surface to volume becomes very large. To avoid the lengthy and difficult technique of elutriation it has been proposed to estimate the size distribution below 200 mesh from various probability formulas. Such a procedure is at best an engineering approximation; at worst it is a mere guess. Some time ago Dr. V. H. Gottschalk2 found that the coercive forces of magnetite powders were directly proportional to the surface area, regardless of size distribution. It was at once apparent that this furnished a method for determining grinding efficiency quickly and accurately. The only requirement was a single determination of the relation between the work input of the Gross-Zimmerley drop-weight machine and the coercive force of the resultant crushed magnetite. For this purpose Ural Mountain magnetite in definite octahedra was

Jan 1, 1939

DURING the month of March there was some lifting of the veil, revealing somewhat of the maelstrom in the economics and politics of the world. Great Britain was in throes of political controversy, with threats of resignation by Lloyd George and a general election to ensue. Ireland was uneasy with internecine squabbles. The leaders of the opposing sides have been summoned to London for a conference which Parlia-ment believes offers the only hope of a solution of the present difficulties. France, awakening more and more to grim realities, learned of a budget for 1922 calling for more than 50 billion francs, or nearly one-third of the estimated national production, with the prospect that after this deduction is made there will be nothing left over what is required for the immediate support of the, people, and that on a reduced scale. Germany, although hard at work, found itself coming closer and closer to financial collapse and repeated its intimations that it would be unable to keep up with the provisional payments of 31 million gold marks to the Reparations Commission every 10 days as arranged at Cannes. Russia suffered more acutely from the famine and there were evidences of political insubordination among the Ukrainians. Egypt was in trouble arising from determination to win independence. About the middle of March the complete independence of Egypt was established and that country passed into somewhat the same relation-ship toward Great Britain that Panama has to the United States. At the head of the Adriatic, Fiume came into notice again with disorders threatening to produce conflict between Italy and Jugoslavia. In the Near East there were forebodings of trouble through resumption this spring. of the war between Greece and Turkey.

Jan 4, 1922

By R. S. Dean

The careful work of Gross and Zimmerleyl has established the fact that the energy actually used in grinding is proportional to the new surface produced. This confirmation of Rittinger's law was made by crushing quartz in a frictionless drop-weight machine and determining the surface of the quartz by its rate of solution in hydrofluoric acid. The details of this procedure have been described adequately elsewhere and need not be repeated here. The resultant data furnish the only available basis for comparing accurately the efficiency of grinding machines. This method is so cumbersome experimentally that it has been little used. As an alternative all sorts of approximations have been proposed. The best of these is complete size analysis by sieving and elutria-tion. Such procedure is very lengthy and difficult to carry out accurately. Furthermore, any sizing method becomes very inaccurate for determining surface with very fine sizes where the ratio of surface to volume becomes very large. To avoid the lengthy and difficult technique of elutriation it has been proposed to estimate the size distribution below 200 mesh from various probability formulas. Such a procedure is at best an engineering approximation; at worst it is a mere guess. Some time ago Dr. V. H. Gottschalk2 found that the coercive forces of magnetite powders were directly proportional to the surface area, regardless of size distribution. It was at once apparent that this furnished a method for determining grinding efficiency quickly and accurately. The only requirement was a single determination of the relation between the work input of the Gross-Zimmerley drop-weight machine and the coercive force of the resultant crushed magnetite. For this purpose Ural Mountain magnetite in definite octahedra was

Jan 1, 1939

By P. D. Hunt, B. Tani, M. G. Chasanov, R. Schablaske

The Zn-Vphase diagram was studied by thermal. metallographic, X-ray, and sampling techniques. Three ternary phase equilibria were observed: Mutual solid solubilities in vanadium and zinc appear to be negligible. The liquidus line is retrograde from 670° to 756°C. 1 HE only information in the literature relating to the Zn-V system was a study of corrosion of vanadium by liquid zinc' and an examination of the effectiveness of zinc coatings in protecting vanadium-base alloys from oxidation at high temperatures.2 Establishment of the Zn-V phase diagram was undertaken as part of a study of transition metal solubilities in liquid metal solvents. Chemical, metallographic, thermal, and X-ray diffraction analyses were used to determine the diagram. MATERIALS AND EXPERIMENTAL PROCEDURES Vanadium (99.86 pct) in the form of powder and small chips was employed. Stick zinc (99.99 pct; major impurities: 10 to 15 ppm Pb and 20 ppm Cu) was used in the liquidus determinations and thermal analyses; zinc powder (98.80 pct) was used to prepare intermediate compositions. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The apparatus and sampling techniques were similar to those described by Martin, et al.3 The entire metal sample was dissolved to preclude analytical errors due to segregation on cooling. Vanadium was determined amperometrically, using iron (11) as the titrant,4 to an estimated accuracy of 1 pct. Standard techniques of thermal analysis were employed to examine alloy specimens contained in alumina crucibles under helium. Heating and cooling rates were about 1°C per min. At least five heating and cooling cycles over the range 420° to 700°C were performed for each of two Zn-15 pct V alloys. A Zn-0.2 pct V alloy was used in the determination of the eutectic temperature. The separation of intermediate phases from zinc-rich alloys was carried out by selective leaching with ammonium nitrate solutions. For further investigation of intermediate phases 1/4 in. diam powder compacts were prepared by pressing at 80,000 psi and were annealed in argon at 415" to 450°C for 10 days. Larger quantities of intermediate phases were prepared in sealed tantalum capsules heated in a rocking furnace. Temperatures were determined to an estimated accuracy of 0.5°C with a Pt/Pt-10 pct Rh thermo-

Jan 1, 1963

By M. V. Lowry

This paper outlines the economic considerations that led to the recent installation of a thickener at St. Joseph LeadCo.'s Balmat, N.Y. mill. To incorporate storage of concentrates, they decided upon a single, unusually deep tank to be used for both storage and thickening. The abnormally high rake lift required was achieved by the novel feature of having the entire drive platform raise and lower. Initial operating problems are described along with the satisfactory solutions. Total costs for concentrate handling before and after installation of the storage thickeners are compared. In Northern New York State, the St. Joseph Lead Co. conducts a 2100 tpd zinc mining and milling operation at its Balmat Plant. Conventional crushing, grinding, and flotation is used to produce a zinc concentrate. For 32 years, from 1930 through 1962, the plant operated with the concentrates going directly from flotation to the filtering, drying, and loading facilities. All of the concentrate handling equipment, therefore, had to operate 24 hrs per day. It also had to accommodate wide fluctuations in tonnage, due to variations in the grade of ore. Many problems were thereby encountered in filtering and drying, but it was never concluded that the cost could be justified for installing a conventional, large diameter thickener. Finally, in 1963, they installed an unconventional thickener that is unusual in several respects. The tank depth is 16 ft instead of the normal 8 ft. The rakes are raised and lowered by having the main drive gear located on a movable platform. Automatic controls are programmed to raise the drive platform and rakes during one shift of storage. During the next two shifts of withdrawal, the controls are programmed to lower the drive platform and rakes. After three years of operating this unique storage-thickener, the conclusion is that a correct choice was made from several alternative schemes for storing concentrates. The various considerations involved in the final selection will here be analyzed, and the design features and installation details will be de- scribed. Operating problems and modifications made to the equipment will next be considered, and finally the effects upon filtering, drying, and loading will be reported. SELECTION CONSIDERATIONS Even without a thickener, concentrate handling had become reasonably efficient at the Balmat Mill by the year 1962. A tonnage that varied between 6 and 25 tph was being handled fairly satisfactorily. The filter cake moisture of 8%% seemed quite respectable, except that two large filters were usually in service. Three filters often had to be operated in order to prevent excessive filter overflow with consequent loss of values. This situation occurred when zinc concentrates from flotation exceeded 20 tph and when filter cloth blinding developed. Over the years, numerous small improvements had been effected, such as: selection of a filter cloth with better flow characteristics; addition of flocculant to the filter feed; and, in 1953, the smallest of three drum filters was replaced by a five disc, 8' 10" diam filter with a bottom agitator and snap blow. As another example of fairly efficient operation, the oil-fired dryer was doing a seemingly satisfactory job of further reducing the moisture content to an average of 3%. However, there were often considerable dust losses when the tonnage suddenly dropped off to 6 tph. At high tonnage rates, the resulting high moistures of 4% and 5% caused difficulties due to concentrates sticking and freezing in chutes leading to the box car loaders. (Drying of concentrates is justified because of the high freight rate for the long shipping distance to the company owned smelter at Josephtown, Pa. near Pittsburgh.) It was long realized that installation of a thickener would permit the subsequent steps of concentrate handling to proceed more smoothly and would alleviate the problems existing in the filtering, drying, and loading operations. It was also realized that even a slightly lower filter cake moisture could mean considerable savings in fuel oil. However, all these factors were never quite sufficient to warrant the expense of a thickener until three more considerations were added to the picture. First, the advent of flocculants meant that a thickener of relatively small area could now be considered. Secondly, a complete renovation of the zinc flotation circuit was made between 1957 and 1961. The

Jan 1, 1967

By J. B. Austin

IN developing a consistent picture of the thermal expansion of the commercial chromium steels, which cover a range of carbon contents, it is desirable to know the expansion in the limiting case of the binary, carbon-free, iron-chromium alloys. We have, therefore, determined the thermal expansion of a series of five special alloys, ranging in chromium content from 3 to 10.5 per cent, with not more than 0.03 per cent carbon, over a temperature range extending beyond the transformation region; this low carbon content enables us to draw reasonably reliable conclusions as to the behavior of the carbon-free system. Moreover, the measure-ments serve to determine the beginning and the end of the alpha-gamma transformation; and they emphasize once more the fact that a transforma-tion temperature determined by any method in which the specimen is cooled at an appreciable rate is apt to be seriously in error, particularly if the metal contains a transformation-retarding element such as chro-mium or managanese. The lag, or undercooling, observed at the ? - a transformation is explained in terms of the influence of temperature on transformation velocity; the rather unusual shape of the ? loop is attributed to a change with temperature and with composition of the distribution of chromium between the alpha-iron and gamma-iron solid solutions. The exact composition of the alloys which were obtained through the courtesy of Dr. W. Rohn, of the Heraeus Vakuumschmelze A-G., is given in Table 1. Determinations of the linear thermal expansion and of transformation temperature were carried out in the vacuum dila-tometer previously described,1 using a rate of heating and of cooling of 3.0° to 3.5° per minute unless otherwise stated. Magnetic susceptibility, which was measured in studying the rate of transformation, was determined with a magnetic balance, which also has been described.2

Jan 1, 1935

By J. B. Austin, R. H. H. Pierce

IN developing a consistent picture of the thermal expansion of the commercial chromium steels, which cover a range of, carbon contents, it is desirable to know the expansion in the limiting case of the binary, carbon-free, iron-chromium alloys. We have, therefore, determined the thermal expansion of a series of five special alloys, ranging in chromium content from 3 to 10.5 per cent, with not more than 0.03 per cent carbon, over a temperature range extending beyond the transformation region; this low carbon content enables us to draw reasonably reliable conclusions as to the behavior of the carbon-free system. Moreover, the measurements serve to determine the beginning and the end of the alpha-gamma transformation; and they emphasize once more the fact that a transformation temperature determined by any method in which the specimen is .cooled at an appreciable rate is apt to be seriously in error, particularly if the metal contains a transformation-retarding element such as chromium or managanese. The lag, or undercooling, observed at the ?-a transformation is explained in terms of the influence of temperature on transformation velocity; the rather unusual shape of the ? loop is attributed to a change with temperature and with composition of the distribution of chromium between the alpha-iron and gamma-iron solid solutions. The exact composition of the alloys which were obtained through the courtesy of Dr. W. Rohn, of the Heraeus Vakuumschmelze A-G., is given in Table 1. Determinations of the linear thermal expansion and of transformation temperature were carried out in the vacuum dilatometer previously described,1 using a rate of heating and of cooling of 3.0° to 3.5° per minute unless otherwise stated. Magnetic susceptibility, which was measured in studying the rate of transformation, was determined with a magnetic balance, which also has. been described.2

Jan 1, 1935

By Clarence Fenner

THE manufacture of optical glass is a process that demands careful regulation and control at all stages in order that satisfactory results may be obtained. The product, to serve its purpose, must meet stringent requirements, which can be assured only by careful procedure in manufacture. During the greater part of the time that a pot of glass is in the furnace, temperatures should be kept within certain rather narrow limits; a departure on either side is likely to be detrimental to the glass and may result in total loss. If the temperature during melting and fining be low, the melt is likely not to fine properly and the glass will contain quantities of bubbles, or "seed," or it may become milky and unfit for use; too high a temperature, on the other hand, is severe on the pot and may cause it to leak or cast stones, or the increased solution of pot material in the melt may acid to the color of the glass and decrease its transmission. Moreover, variations in the working temperature will mean variations in the amount of selective volatilization and, consequently, variations in optical properties from pot to pot. Furthermore, in the closing stages of furnace treatment, the melt is cooled until a certain degree of stiffness is attained, when the pot is withdrawn. The quality of the glass-its freedom from striae and bubbles-will depend in large measure on whether the temperature to which cooling has been carried is suitable. For each type of glass there is a narrowly restricted range of temperature to which each pot of the given type should be cooled before withdrawal. A quick and reliable method of measuring temperatures is, therefore, of the first importance. In the optical-glass work conducted by the staff of the Geophysical Laboratory during the period of the war, much attention was given to the clatter of determining what methods would meet the requirements. This article will deal with these investigations and with the application of the results to actual practice at various plants. At the. time that the work of the Geophysical Laboratory was begun at the Bausch & Lomb plant, each melting furnace was equipped with

Jan 7, 1919

By J. M. Morris

The point to be made most clear in this paper is the economic value of flotation in the Benguet mill flow sheet. It is rather a statement of effect with no attempt at a technical explanation of the cause. Certain well-known, easily understood reagents, mechanisms and principles have been adapted to the conditions at Benguet, and have proved to be more successful than was demonstrated in the laboratory. The mechanical and metallurgical development of this particular operation was arrived at by trial and error, with fortunately very little error. Changes were slow, of necessity, which in the end proved a blessing in that time was afforded for observation and analysis of the disturbing factors; and as a result each change was a definite step towards higher efficiency. Many of these steps were unpredictable from laboratory work because of the varied and differing characteristics of ores met with in daily operation of the mill, which were practically impossible to reproduce on a laboratory scale. The Benguet mill receives daily ores that differ as much as if they were delivered from three different properties. There is first the surface and upper-level zone, which produces an oxidized secondary ore containing considerable iron oxide, manganese oxide and some organic matter. Formerly, most of this ore consisted of very soft fill with some hard rock mixed in. It also contained an unusual amount of iron and aluminum sulfate, which formed hydrates upon entering the alkaline cyanide solution and caused excessive frothing. When flotation was introduced in the Benguet mill the general characteristics of this upper-level ore had changed considerably, in that it was practically all newly mined, fairly hard ore. It still contained many of the same disturbing elements, but was somewhat simpler to treat than formerly. The small proportion of fines is still troublesome in flotation, and plant practice probably does not show more than 80 per cent extraction on this small portion of the ore. No definite figure on this is available, as this particular ore is delivered at irregular intervals

Jan 1, 1939

By J. M. Morris

The point to be made most clear in this paper is the economic value of flotation in the Benguet mill flow sheet. It is rather a statement of effect with no attempt at a technical explanation of the cause. Certain well-known, easily understood reagents, mechanisms and principles have been adapted to the conditions at Benguet, and have proved to be more successful than was demonstrated in the laboratory. The mechanical and metallurgical development of this particular operation was arrived at by trial and error, with fortunately very little error. Changes were slow, of necessity, which in the end proved a blessing in that time was afforded for observation and analysis of the disturbing factors; and as a result each change was a definite step towards higher efficiency. Many of these steps were unpredictable from laboratory work because of the varied and differing characteristics of ores met with in daily operation of the mill, which were practically impossible to reproduce on a laboratory scale. The Benguet mill receives daily ores that differ as much as if they were delivered from three different properties. There is first the surface and upper-level zone, which produces an oxidized secondary ore containing considerable iron oxide, manganese oxide and some organic matter. Formerly, most of this ore consisted of very soft fill with some hard rock mixed in. It also contained an unusual amount of iron and aluminum sulfate, which formed hydrates upon entering the alkaline cyanide solution and caused excessive frothing. When flotation was introduced in the Benguet mill the general characteristics of this upper-level ore had changed considerably, in that it was practically all newly mined, fairly hard ore. It still contained many of the same disturbing elements, but was somewhat simpler to treat than formerly. The small proportion of fines is still troublesome in flotation, and plant practice probably does not show more than 80 per cent extraction on this small portion of the ore. No definite figure on this is available, as this particular ore is delivered at irregular intervals

Jan 1, 1939

By R. A. F. Penrose

I. INTRODUCTION. THE superficial alteration of ore-deposits is a recognized principle of geology, in the same way as is the superficial alteration of any of the common rocks. Its importance in some classes of ore-deposits is also well understood, as in many precious-metal deposits; while in other classes, its importance has been proved in individual cases, as in the Lake Superior iron-deposits. The causes and effects of superficial alteration in many classes of deposits, however, are not so generally understood; and it is the object of the present paper to show that such changes almost invariably give rise to exceedingly important chemical and physical phenomena, while in many deposits, the question as to whether they can or cannot be profitably worked depends largely on the extent and character of this alteration. The various treatises on ore-deposits published in the United States and Europe make frequent mention of superficial alteration, but have not treated the subject fully. As early as 1554, however, before which time but little accurate information was had on the geologic nature of ore-deposits, Prof. J. D. Whitney in his classic volume, The Metallic Wealth of the United States, describes the alteration-products, or gossans, in certain deposits and mentions others. On the more purely chemical side of the question, the work of Bischof, Daubrée, Roth, Rose, Hunt, Breithaupt, Blum, Julien, Deville, Debray, Volger, Moissan, Fremy, Lévy, Fouqué, and others has afforded much valuable information and many useful suggestions. The chemical principles brought out by these various authors have been applied, to a certain extent, to the solution of the phenomena of

Jan 1, 1913

By Rebecca Mae Summer

Increasing urbanization and industrial activity require increased supplies of sand and gravel. This means expanded surface mining and despoiled land near population centers. Highly competitive land use demands justify serious consideration of premining planning for multiple land use and reclamation concurrent with mining. 1-5 Formulating solutions to environmentally and economically sound uses requires a comprehensive approach based on properties of the natural resource base--geology, soils, and water. A study of sand and gravel mining within Pleistocene-Holocene fluvial deposits in Colorado County. Texas [(Fig. 1)] illustrates how physical limitations imposed by the resource base are determined.6,7 Data from drillers, logs of water wells, test boreholes, field observations, and laboratory analyses are used to evaluate these physical controls. Knowledge of the thickness and composition of overburden aids in developing optimum reclamation and revegetation plans. Most of the overburden in the study area [(Fig. 2, 3)] is a clayey mud with variable amounts of silt and fine sand. A comparative textural analysis of overburden and native soil is used to assess changes incurred by mining and for evaluating other physical characteristics, e.g., ability to support crops, permeability. and shrink-swell potential. Textures are correlated with soil types found in the area [(Table 1)] to get an approximation of probable surface properties expected from these mined materials. Results of textural analyses [(Table 2)] indicate that separating topsoils from overburden during mining is not necessary because the range of overburden textures is about that of native soils. However, more data is needed on nutrient deficiencies to evaluate fertilizer requirements for successful revegetation.*6

Jan 1, 1979

By R. F. Lynch, J. D. Wood

The Al-1.0 pct Mg alloy 565 7 was studied using optical microscopy and electron microprobe X-ray analysis. Constituent particles were found to exist inter-dendritically in the as-cast material in a region of precipitate free a -aluminum. Five phases besides a fine precipitate and a-Al were identified in the cast structure: Fel3, Fe2Al7, Mg2Al3, CUMgAl2, and Cu2FeAl7. Thermal treatments conducted for 100 hr at 1180°, 1130°, 1080°, 1030°, 980°, and 880° F revealed a general dissolution and spheroidization of the in-terdendritic constituent network observed in the cast structure. The principal constituents present in the thermally treated structures were FeAl3 and Fe2Al7 with the relative amount of Fe2A17 to FeAl3 increasing with a decrease in the treatment temperature. The phases Present in the wrought structure were identical to those observed after the thermal treatments, with the constituent particles strung out in the direction of rolling. ALLOY 5657 is a nonheat-treatable commercial purity Al-1.0 pct Mg alloy utilized extensively because of its bright finishing characteristics. This investigation was conducted to determine the constituents present in 5657 alloy, and to study the effect of extended thermal treatments on morphology. Numerous studies have been carried out to establish the equilibrium diagrams for various aluminum systems,1-3 with phase identification based on X-ray analysis, morphology, and the etching response of relatively large particles. Phragmen4 conducted a study of the phases in aluminum eutectic systems and compiled a "corrected" table of etching responses, drawing on his work plus that of Schrader,5 Keller and Wilcox,6 and Mondolfo.7 A review of the original work of Keller and Wilcox, and Mondolfo, which was concerned with the constituents found in commercial alloys, reveals that in numerous cases their etching responses differ from those reported by Phragmen and from each other. These inconsistencies may occur because a specific constituent will react to a given etch in a varying manner depending upon its size, the elements dissolved in the phase, the other constituents surrounding a phase, and the solute content of the matrix. Work with a commercial orientation was conducted on alloys 2024 and 3003 by Sperry8,9 and on alloy 3003 by Barker,10 where the relationship between the phase diagram and the nonequilibrium structure of an alloy was examined. Backerud11 investigated the A1-Fe binary system and found that at high cooling rates the equilibrium eutectic reaction forming a-A1 and FeA13 is replaced by another lower temperature eutectic reaction forming a-A1 and metastable FeAl6, a constituent first identified by Hollingsworth et al.12 Most of the above mentioned studies were conducted on materials having a significantly greater alloy content than 5657 alloy, where the relatively small size and sparse distribution of second phase particles hinders the process of identifying constituents. EXPERIMENTAL PROCEDURE Material with a composition as given in Table I was examined in the as-direct chill cast, hot rolled and cold rolled conditions, and after thermal treatment of the cast structure. Thermal treatments were terminated by a water quench. Microscopic examination was conducted under various lighting conditions following the application of standard etchants as specified in Table 11. A semi-quantitative electron microprobe X-ray analysis was conducted for Al, Mg, Fe, Cu, Si, Zn, and Ti. RESULTS AND DISCUSSION Microstructure of the As-Cast Material. Particles of second phase material were found to exist inter-dendritically, principally in regions of precipitate free a-Al, as illustrated in Fig. 1. Adjacent to the ingot edge was a region of inverse segregation, resulting in an increased amount of second phase material containing large sized particles which aided in phase identification. Phase Identification. Cast Structure. Five phases besides a-Al and a fine precipitate were identified using optical microscopy and electron microprobe X-ray analysis, as presented in Tables II and III, respectively. FeA13 and Fe2A17 are often found with Fe2A17 forming a sheath around the core of FeAl3, resulting from an incomplete peritectoid reaction. These phases have a nearly identical appearance under white light, although they are easily differentiated under crossed polarizers, as characteristically illustrated in Figs. 2(a) and 2(b), respectively. Microprobe analysis con-

Jan 1, 1970