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By H. Biloni, B. Chalmers

Metallographic studies of the segregation of solute in and near the surfaces of chill-cast alloys have shown that, under sufficiently severe conditions, nucleation on the cold mold surface is followed by the formation of a disc of solid of the same composition as the liquid. This disc is surrounded by two concentric rings in which the concentration first decreases and then increases. The discs and rings are surrounded by a region in which arms of low solute concentration separate regions of high concentration. These arms start at the periphery of the outer ring and are initially radial; they make a gradual curved transition from the radial direction to a crystallographic direction. A normal dendritic substrcture is established beyond the position at which the arms have become crystallographically aligned. When the cooling is less severe, the disc becomes less irregular in shape and has a concentration minimum at the center. The term "Predendritic" is proposed for these transitions. A qualitative explanation is outlined for the phenomena observed at the surface and in the equiaxed region of the ingots. It is well-established1-' that the normal mode of solidification for alloys under most conditions is dendritic. A characteristic of dendritic solidification is the growth of rods or plates in specific crys-tallographic directions. The remaining liquid solidifies later, usually with a higher concentration of solute than the original liquid. Very little is known, however, about the transition from a crystal nucleus until the dendritic pattern is established. It is clear that there must be a transition because the nucleus is much smaller than the characteristic spacings found in the "steady-state" structure. And it also seems clear that the initial conditions must be important since the undercooling existing during the nucleation of the grains has a remarkable influence upon the grain size4 and the segregation pattern. The present paper reports a study of the micro-segregation in regions where crystals have nucleated, and the conclusions that can be drawn regarding the early stages of growth, in connection with the details of the solidification process. Aluminum of 99.993 purity, A1-Cu alloys containing 0.5 to 20 wt pct Cu, and Pb-Sn alloys with 5 wt pct Sn were cast and examined metallographically at the as-cast surface, close to the surface, and in the interior after casting. The alloys were cast from controlled temperatures against surfaces at different temperatures ranging from room temperature to approximately the liquidus temperature of the alloy. The surfaces were, in various experiments, graphite, stainless steel, copper, and aluminum. The methods used for metallographic examination were as follows. 1) The Nomarski phase contrast interferometer6 was used to obtain information on the topography of the as-cast surface. 2) The distribution of any solute present in A1 99.993 pct and copper in the A1-Cu alloys was studied by the anodic film technique originated by Lacombe and Mouflard7 and previously applied in the study of the solidification of aluminum by Biloni.8 The electropolished surface of the specimen is anodized under controlled conditions so that the thickness of the oxide film and therefore the interference colors under white light are sensitive to the local composition. This technique was applied to the as-cast surfaces and to metallographically prepared surfaces from the interior. 3) If in Al-Cu alloys, the surface is anodically oxidized for several minutes, instead of seconds as in the color-film technique, the copper segregation is outlined by a different level with respect to the matrix. This method is less sensitive but complementary to that for the color films. 4) The distribution of copper revealed and mapped by the metallographic techniques was confirmed by electron probe. 5) In samples with high concentration of copper, evidence for the copper distribution could be seen optically after electropolishing.

Jan 1, 1965

By Louis Huber

THE Liberty tunnels extend through a very steep hill in Pittsburgh (locally called Mount Washington) for a distance of slightly over a mile. The two tunnels parallel each other and are 59 ft. apart, center to center (Fig. 1). They are for vehicular traffic, and in each there is ample space for two lines of vehicles. Northbound traffic, towards downtown Pitts- FIG. I.-NORTH PORTAL OF LIBERTY TUNNELS. NOTE THE WINDBREAK AT END OFEAST TUNNEL. burgh, is confined to the east tunnel and southbound traffic to the west tunnel. The South Hills residential district is separated from downtown Pittsburgh by Mount Washington, a steeply rising escarpment south of and adjacent to the Monongahela River. The Mount Washington district immediately south of the Monongahela River has been reached, for many

Jan 1, 1927

By J. L. Kenty, J. P. Hirth

The concept of a critical super saturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, is discussed with reference to vapor-solid nucleation. The necessary and sufficient conditions deduced for observations of this type of behavior are: 1) the nucleation rate must exhibit a sharp dependence on super saturation, 2) the growth rate must be sufficiently large that nuclei become observable in the time period of the experiment, and 3) the number of highly preferred nucleation sites must be small. Experiments reveal that the nucleation of silver on sodium chloride is visually detectable at all experimentally accessible super saturations and does not exhibit critical nucleation behavior. Failure to observe a critical super saturation is attributed to the insensitivity of nucleation rate to supersaturation as a consequence of the particular values of the contact angle and the surface free energy for this system. THE concept of a critical supersaturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, arises naturally in homogeneous nucleation theory. Experimentally this type of behavior has been found by Volmer1 and others for water and other low surface tension liquids, as reviewed by several authors.2'3 The same type of behavior has been predicted and observed for heterogeneous nucleation of solids by Yang et al.4 and others,596 as also recently reviewed.2,7,8 In the work reported here on the heterogeneous nucleation of silver on NaC1, however, no critical super-saturation was found. Similar observations have been made recently for other systems.9-11 These results led to a reexamination of nucleation theory which revealed that there are conditions for which critical behavior is not predicted, either for homogeneous or heterogeneous nucleation. Although heterogeneous nucleation is of primary importance in this paper, some insight into critical behavior for such a case can be gained by considering homogeneous nucleation. Accordingly both types of nucleation theory are reviewed briefly. The requisite conditions for critical supersaturation behavior are then considered. The experimental results for the nucleation of silver on NaCl are presented and interpreted in terms of the theoretical presentation. REVIEW OF NUCLEATION THEORY There are essentially two approaches to nucleation theory, the so-called classical theory involving the concepts of bulk thermodynamics, and the statistical mechanical theory in which nuclei are regarded as macromolecules. The classical theory is based on the work of Volmer and Weber12,13 and Becker and. Doring14 and has been extended by Pound et al.15 The crucial assumption in the classical theory is that the small clusters or nuclei can be characterized by the same thermodynamic properties as those of the stable bulk phase. Thus, the nuclei are assumed to have a surface free energy, y, and a volume free energy of formation (relative to the vapor phase), ,, identical to that of the bulk. For deposition under low super-saturation conditions, the nuclei are large and this assumption is satisfactory. However, in many cases of interest, the nuclei contain only a few atoms and this assumption is highly questionable. The statistical mechanical models originated, for the specific case of a dimer as the critical nucleus, with the work of Frenkel16 and were extended later to larger sizes by Walton,17,18 Hirth19 and, more recently, Ht Zinsmeister. These models describe the nucleus in terms of a partition function, the estimation of which is tractable for clusters of 2 to 10 atoms, but extremely difficult for clusters larger than 10 atoms. Although the classical and statistical mechanical models are expected to apply for the limiting cases of large and small nuclei, both are uncertain for intermediate sizes. In this paper we shall treat only the classical model, recognizing that it is exact only for large nucleus sizes and regarding it as a phenom-enological description for small nucleus sizes. When analyses of experimental data using bulk properties show the nucleus size to be small, the resulting parameters should be regarded as largely empirical parameters describing the relative nucleation potency of the system. Considerable justification for the continued use of classical theory is provided by its general success in predicting nucleation behavior as a function of supersaturation and temperature. We emphasize that the qualitative features of the statistical mechanical models, particularly the critical super-saturation behavior that is central to the present work, are the same as those of the classical model. Of course, potential energy terms and surface partition functions replace the volume and surface energy terms of the latter model. The most recent versions of classical nucleation theory have been extensively reviewed.2,3,7 so that only the results are presented here. For homogeneous nucleation of a condensed phase from the vapor phase, the volume free energy change is ?Gv=vrT = =^ln£ [1] where v is the molecular volume of the condensing species. The supersaturation ratio,

Jan 1, 1970

By A. W. H. Morris, G. H. Laurie, J. N. Pratt

Using- galvanic cells of the form Sn(liq)/Sn" (LiCl-KC1-SnCl,)/Sn-Ag (alloy), measurements have been made of relative thermodynamic properties of the a, C, E, and liquid phases of the Ag-Sn alloy system. Partial heats of solution of the components in the liquid alloys lzave also been observed by direct cal-orimetric measurement in an isoperibol calorimeter. The thermodynanzic quantities are disczlssed in relation to structural and other properties and the existence of anomalous minor fluctuations in the partial heats and entropies of solution in liquid alloys is tentatively suggested. In the course of a recent electro motive-force study of the thermodynamic properties of Sn-Ag-Pd liquids,' some measurements were also performed on the Ag-Sn binary system. Most previous thermodynamic studies of this system have been concerned with the liquid state. Measurements confined to the limiting heat of solution of silver in liquid tin have been made by many calorimetric workers2 while high-temperature calorimetric measurements of the heats of formation of the full range of liquid alloys are reported in the early work of Kawakami~ (1323°K) and more recently by Wittig and Gehrin~(1248°K). Electromotive-force studies on liquid alloys have been made by Yanko, Drake, and Hovorka' (606" to 686°K; 86 to 99.4 at. pct Sn) and by Frantik and Mc Donald' (900°K; 30 to 90 at. pct Sn). The only known measurements on the solid state are of heats of formation of the a, £, and c phases; these values were obtained using tin-solution calorimetry, at 723"K, by Kleppa,~ whose investigation also yielded heats of formation of liquid alloys containing more than 64 at. pct Sn. The present experiments on the Ag-Sn alloys include a re-examination of the liquid phase and, because of the dearth of free-energy data for the solid state, attempted measurements on the a, c, and E phases. The principal new feature of electromotive-force results obtained for the liquid phase was an indication of anomalous fluctuations in the partial heats and entropies of solution of tin at certain compositions. However, since the values for these thermodynamic quantities were determined from the temperature coefficients of cell potentials, which are commonly subject to considerable error, confirmation by calorimetric measurements was considered desirable. A detailed investigation of the partial heats of solution of the components in the binary liquids was made using a liquid metal solution calorimeter. I) GALVANIC CELL STUDIES a) Experimental Details. Measurements were made, as a function of alloy composition and temperature, of the potentials of reversible galvanic cells of the form: ~n(liq)/~n++/~n-Ag (solid or liquid alloy) Details of the apparatus and experimental techniques have been given elsewhere.' so that a brief account will suffice here. Molten salt, 58 mole pct LiC1-42 mole pct KC1, containing small amounts (1 to 2 mole pct) of stannous chloride was used as the electrolyte. The salts were dehydrated by pre-electrolysis and vacuum -drying techniques. Cells were established under an argon atmosphere by immersing tin and alloy electrodes in the molten salt contained in a large silica tube, heated in a vertical resistance furnace. The tube was sealed at the top by a head plate provided with openings permitting the simultaneous insertion of six electrodes, a central thermocouple sheath, and connections to vacuum and argon lines. Temperatures were controlled to *0.2"C over prolonged periods, with maximum variation over the electrodes at any time of 0.l°C. Temperatures were measured with a standardized Pt/13 pct Rh-Pt couple. The electromotive force of this and the cell potentials were measured on a Cambridge Vernier potentiometer and short-period galvanometer. Alloys were prepared from Pass "S" tin (99.999 pct) and Johnson-Matthey high-purity silver (99.999 pct) by melting in evacuated silica capsules and quenching in cold water. For liquid phase experiments, pieces of the resulting alloys were remelted into prepared silica electrode units, while solid electrodes were prepared by remelting into 3-mm bore tubing, inserting a cleaned molybdenum lead wire, and quenching to produce uniform rods about 3 cm in length, with soundly attached leads. In all cases remelting was done under an argon atmosphere. The solid electrodes were subsequently annealed in evacu ated silica tubes for 14 days at about 20°C below the solidus and quenched. Analyses showed that these techniques produced uniform electrodes with no significant change from weighed out compositions. b) Results and Discussion. Measurements were made on about forty alloys in the solid and liquid states, over varying ranges of temperature between 550" and 1050°K. Stable, mutually consistent, and reproducible electromotive-force data were obtained with most liquid alloys and these are shown in Fig. 1. Investigations were extended below the liquidus tem-

Jan 1, 1967

By H. Shaw

GRAVITATIONAL measurements made by means of the Eötvös torsion balance over any area enable a representation to be obtained of the total gravitational effects over the surface of that area arising from the combination of all sources of gravitational disturbance. The investigation of gravitational anomalies occurring in the upper layers of the earth's crust, in this way, has been attended with considerable success, and, especially in areas in which no undesirable disturbing factors were present, it has been possible to locate geological structures and mineral deposits with remarkable accuracy and also to delineate their confines and to indicate their depth below the surface with a certain amount of precision. Before this can be done successfully, however, it is necessary to determine the gravitational effect arising from all other extraneous .anomalies in order that these may be satisfactorily eliminated. Disturbing features giving rise to these gravitational anomalies may be divided into two classes, according to whether they are situated at or below the surface. The former are determined readily by a detailed leveling of the ground surface, and may be satisfactorily eliminated provided the specific gravity of the terrain material is known, but the latter are generally unknown, and can only be ascertained with difficulty. When, therefore, the observations obtained by means of the Eötvös torsion balance have been corrected for all surface irregularities, known as terrain and topographical effects, there remain residual gravitational values which are due entirely to subterranean conditions. The task of interpreting these results consists in disentangling the various subsurface anomalies, and subsequently in computing and recombining the effects of these various masses in order to verify the interpretation. When the gravitational anomalies are due to large and comparatively simple structures it is a matter of little difficulty to arrive at a satisfactory interpretation of the subterranean conditions, but in more complex areas, where the geological conditions are more complicated and several irregular features exist, the process of disentangling the various constituents of the complex mass arrangement is more difficult and requires the expenditure of considerable time and labor.

Jan 1, 1929

By J. D. Hanawalt, C. E. Nelson, J. A. Peloubet

THE subject of the salt-water corrosion resistance of magnesium alloys is somewhat like that of the pitting of stainless steels, in that it involves a relatively small percentage of the applications but receives a much greater proportion of the publicity. Actually magnesium alloys are in use in many exterior applications as well as interior, with no trouble from corrosion. Magnesium and its alloys have a striking stability against atmospheric attack, being far superior to iron. Specimens exposed unprotected to atmospheric weathering for 10 years show only a superficial surface-film formation. The basic nature of magnesium and of its important alloys is that they are also resistant to the attack of salt water even in an unprotected state, giving substantially no loss in weight after one year of alternate immersion in 3 per cent NaCl solution (Fig. I). This basic behavior is often masked because of the extreme sensitivity of these alloys to certain impurities and combinations of impurities. It is known, and the subject of increasing emphasis, that higher purity leads generally to greater stability for many materials, nonmetallic as well as metallic. However, a review of the literature on the corrosion factors in magnesium alloys shows that almost all researchers worked with base metal in which metallic impurities varied in uncontrolled amounts. The major factor, that of metallic impurities, probably greatly overshadowed the effects of minor ones such as flux inclusions, nonmetallic impurities, porosity, metallographic state, which these researchers presumed to study. In the present investigation the first observation of interest is that whereas magnesium of commercial purity (99.9 per cent pure) has a corrosion rate in alternate immersion in 3 per cent NaCl solution at room temperature of anywhere from 5 to 100 mg. per sq. cm. per day, the corrosion rate of high-purity magnesium is 0.15 ± 0.05 mg. per sq. cm. per day. The principle followed in the experiments was to add to such base magnesium other elements, singly and in combination, in controlled and known amounts and to observe the corrosion behavior of the resulting alloy. These experiments show the existence of what may be called "tolerance limits" of magnesium and some of its alloys for certain impurities. The extremely small percentages of impurities involved and the sharpness of the corrosion discontinuities appear to be quite unpredictable. In order to carry on this work, it was necessary to develop an analysis technique suitable to the problem. In some cases it was necessary quantitatively to analyze impurities to less than 0.001 per cent. The experimental data to be presented are based on observation of about 5000 alloy specimens and on more than 50,000 quantitative analyses. While the primary purpose of this paper is to present the experimentally obtained data on corrosion rates as a function of composition, and particularly to demon-

Jan 1, 1941

By C. A. O’Connell

Surface exploration drilling at Mufulira started in 1928, with drillhole No. 1 intersecting ore near the eastern fringe of the deposit. Subsequent drilling along strike intersected ore until the western fringe was fixed some 7500 ft west of drillhole No. 1. Further intensive drilling down dip disclosed a large triangle of ore with its apex 3350 ft deep. It contained approximately 11 6 million tons of ore at 4.41% total copper in three superimposed orebodies. The east and west limits of the orebodies were presumed to have a pronounced rake to the north with a strike length of 8000 ft. Subsequent exploration underground seemed to bear out this presumption to the 1150 ft level. In 1947, attention was directed to the area west of the known orebodies in conjunction with plans for increased production and increased depth of the mine workings.

Jan 12, 1962

By Robert Glass Cleland

THE DEATH of William E. Dodge occurred at a time when, all unwittingly, the company in which he had so long been the dominant factor was about to break with its old practices, its old traditions, its old interests, and transfer its major activities three fourths of the way across the continent and engage in an enterprise that differed almost as much from the original Phelps Dodge undertakings as the rough, arid mountains of the new region differed from the green hills and valleys of New England. To understand the effect of this transformation upon the fortunes of Phelps Dodge, one must change the setting of the present narrative from the familiar locale of the Atlantic seaboard to the land of "distance, silence, and solitude," that men called Arizona. In 1880 that Territory was one of the last frontiers of the Old West. To the Spaniards it had been a land of mystery and fable, the limit of the King's settlements, the far edge of the rim of Christendom. Through it Coronado; in a vain effort to find the fabulous Cities of Cibola, had led "the most brilliant company ever assembled in the Indies to go in search of new lands." Below its southern border, Father Kino, the "steel-thewed" Jesuit described by his

Jan 1, 1952

By D. J. Rose, W. M. Armstrong, A. C. D. Chaklader

The wetiability of single crystals of MgO by specimens of vacuum-cast iron was studied using the sessile drop technique in vacuo at 1550ºC. Formation of FeO at the liquid-vapor interface caused the contact angle (6) to decrease from 117 to 65 deg during the first minute. After cooling, all specimens possessed a peculiar annular interfacial deposit of Fe,O,. Within the annulus the interface showed no sign of chemical attack. Chemical reaction occurred where the iron was alloyed with Ti, V, Cr, Nb(Cb), Ta, cmd Zr. Vnriation of 6 with alloy concentration was studied. Although vanadium md chromium improved the wettability of MgO by iron, the effect of Zr, Ti, Nb, and Ta was indeterminable because the 8 derived from sessile drop considerations was that of the metal against a restrictive peripheral volume of liquid oxide wetting the substrate. INTEREST in the nature of metal-ceramic interactions has been stimulated by progressive development of metal-ceramic combinations. One of the more valuable methods used for bond investigation is the sessile drop technique. Recent attempts to improve wettability through solute additions to the drop have revealed that the solute may a) react with the oxide creating new compounds at the solid-liquid interface, b) adsorb at the interface in a monolayer formation, or c) distribute throughout the drop uniformly causing no wettability variation. This work, part m in a series1,2 of investigations of interface reactions between metals and ceramics, embraces a study of the Fe-MgO system. MgO possesses a large negative free energy of formation (-173 kcal per g mole 0, at 1550ºC) compared to FeO at this temperature (-73 kcal per g mole 02). Hence the electronegativity difference between the drop and substrate allows selection from an extensive group of metal solutes with intermediate electronegativity differences that would, in the absence of chemical reactions, be expected to adsorb pre- ferentially at the solid-liquid interface. However, the high oxygen pressure of MgO in vacuo creates an oxidation environment which influences the solute behavior. Recent studies of the Fe-MgO systemJ74 have been restricted by chemical reactions that obscured observations. In view of the current interest in liquid-phase sintering of metal-ceramic combinations under partial oxidizing conditions,5 a more comprehensive study of the Fe-MgO system seemed beneficial. EXPERIMENTAL PROCEDURE 1) Specimen Preparation. Optical-grade MgO single crystals and Ferrovac vacuum-cast iron were used in all experiments. A spectrographic analysis of the iron indicated 0.008 C, 0.05 V, 0.005 Mo, 0.01 Ti, 0.002 S, 0.01 Cr, 0.001 Mg, 0.01 Si, 0.003 A1 (wt pct). The MgO crystals were cleaved along (100) planes into plates approximately 20 by 20 by 1 mm. Following annealing in vactto at 1100°C for 3 hr, surface irregularities were removed by a chemical etch in phosphoric acid at 100°C. The iron rod was machined into small cylinders approximately 0.250 in. in diam and length and these were carefully cleaned in organic and acidic solutions to remove surface impurities. All specimens were weighed to the nearest 0.1 mg. 2) Apparatus. The apparatus described in detail by previous authors1,2 was modified for this work. A Polaroid Land Camera was incorporated into the optical system so that drop measurements at ten-second intervals after melting were possible with ultra-high-speed self-develop ing film. 3) Procedure. The iron cylinders were placed upright on the MgO plates and positioned in the molybdenum susceptor. After furnace assembly the system was pumped down to a vacuum of 1 µ and flushed with H2 at 800°C. The system was again evacuated to 5 x 10-5 mm of mercury and the temperature raised to 1550°C within 2 min. The molten drops were photographed at appropriate time intervals. TWO min after melting the iron vapor pressure caused gas discharge, or corona, within the tube. The specimens were then slowly cooled to room temperature, sectioned and examined metallographi-cally. X-ray identification of interfacial reaction products was attempted by the powder diffraction technique. Alloying elements (Ti, V, Cr, Zr, Ta, Nb) were added to the iron in various concentrations up

Jan 1, 1963

By Michael Hoch, Seong Kwan Rhee

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

Jan 1, 1964

IN the preceding chapter on thermochemistry and the reactions in and between metal and slag phases and in the following chapter on fuel combustion the main emphasis is placed on the equilibrium or "static" conditions. This equilibrium viewpoint is not concerned with the rate of change in the process or with the mechanisms or paths followed between initial and final states. The questions of just "how it works" and "how fast" belong to the kinetic aspect of any process; their answers are helpful in speeding up or slowing down and thus controlling its operation, and also in understanding its limitations. Any treatment of kinetic factors in the open hearth such as is attempted here and in Chapter 22 must at present be largely qualitative and incomplete. We are only beginning to get quantitative data on rates of reaction and diffusion at high temperatures, as indicated in Chapter 15. Empirical data in the literature on furnace operating rates do not help much to illuminate the details of gas-flow patterns and the complexities of heat flow in the many parts of the furnace system. This chapter is intended to give the reader an introduction to the problems of the flow of gases through the furnace system and the flow of heat in this system. An adequate discussion would require several times the space available here; it is possible here only to outline a few fundamentals and to indicate some of the conditions of heat and gas flow peculiar to the open hearth. Several good general treatments of these subjects may be found in the literature (see references at the end of the chapter). For the designer of open-hearth furnaces, the principles of gas flow are of paramount importance. They are also important to the operation of the process, at least to the extent of a general qualitative picture of the movement of gases in the system. MOTION OF GASES IN FURNACE DUCTS Fluid flow in general can vary between the extremes of laminar or streamline flow with a minimum energy loss, to irregular

Jan 1, 1951

By D. G. F. Hedley, S. N. Muppalaneni, J. W. Roxburgh

A stope and pillar method is used to mine the gently-dipping uranium bearing reefs, to a depth of 1000 m, at Elliot Lake, Ontario. A few isolated rockbursts have been reported in the 11 mines in the area during the first twenty-five years of operation. However, in March 1982 a series of rockbursts were initiated in the old mined-out workings at the Quirke Mine of Rio Algom Ltd. Detailed records of pillar deterioration and size of the affected area were kept both prior and subsequent to the occurrence. Seismic instrumentation was installed before and convergence stations shortly after the start of bursting. Observations indicate that the squat pillars failed violently where- as the slender pillars exhibit a less violent failure mechanism. Floor cracks and heaving are common, but the massive quartzite hanging wall strata is relatively undamaged although some roof falls have occurred due to local structure. The microseismic system accurately locates seismic events to f 20 m within the geophone array and it has been found that an accelerating convergence rate coincides with and in some cases precedes an increase in seismic activity. Displacement discontinuity and boundary element computer models have been used to estimate pillar stresses and areas of high stress concentration in an effort to determine the causes of rockbursts. Mine and pillar stiffness and energy balance concepts are used to explain cases of gradual and sudden pillar failures at Quirke Mine.

Jan 1, 1984

By A. E. Bellis, T. W. Hardy

The problem of heat treating high-speed steel becomes more and more important as the design of cutters becomes more and more complicated in increasing the efficiency of mechanical operatioqs. Hundreds of dollars are spent in the design and manufacture of milling cutters of special form for rapid production of duplicate or interchangeable parts, and then, as the heat treatment is faulty on the one hand, or scientifically executed on the other, the tool fails after a few operations, or its efficiency is greatly increased. The practical operation of giving these complicated tools the right temperature necessary to bring out the best cutting qualities, and at the same time bring-the tool out "clean," is a difficult one and calls for no small amount of skill. In order to be on the safe side the average tool hardener uses a temperature much too low to give the best results with the high-speed steel he uses. In the case of cutters which are finished to a given diameter before hardening, it is impossible to grind the tool after hardening, so that it is essential that the surface be protected from oxidizing or de-carbonizing. It is the aim of this paper to describe some experiments on hardening high-speed stee1, in which metallographic means were used to determine the correct hardening tempcratures. The accompanying table and plates show the results of hardening experiments on five different high-speed steels. The analyses for carbon, tungsten, chromium and vanadium of each steel are given in the accom- . panying table. Six specimens from the same bar of each kind of steel

Jan 1, 1917

By R. L. Doan

WHEN the Plutonium Project was started in the spring of 1942 there was no technology to produce uranium metal of the required purity. Not only was there no such metal available; no one knew how to make it or fabricate it after it was made. Since this time vast technical effort has been ex-pended in the atomic energy field. A short 15 years later the metallurgy of uranium is probably better known than that of any other metal, with the possible exception of steel. At the beginning of the 1942 drive to obtain pure uranium metal the most available raw material was black uranium oxide (U3O8) of about 92 pct purity from the Great Bear Lake region of Canada. It took only three months for the project chemists to develop a process for bringing the purity of this oxide up to 99+ pct and another three months for Mallinckrodt Chemical Co. of St. Louis to build the purification plant and get it into operation. In early summer of 1942 the purified brown oxide (UO2) started moving to the Metal Hydrides Co. in Beverly, Mass., and to the Westinghouse Research Laboratory in Bloomfield, N. J., both of which had been granted Government contracts to try to make pure uranium metal.

Jan 9, 1957

By A. Y. Bethune, W. G. Woolf

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process' for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt's earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.'s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By W. G. Woolf, A. Y. Bethune

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process' for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt's earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.'s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By W. C. Snow

The plant of the Electrolytic Zinc Company of Australasia Limited, situated at Risdon on the estuary of the River Derwent, near Hobart, was designed and erected primarily to produce high-grade zinc from zinc concentrates produced by the mines of Broken Hill, N. S. W. Consequently the metallurgy of the process has been influenced in its development by the peculiar characteristics of the Broken Hill concentrate, which on treatment gives into solution relatively large amounts of cobalt, manganese and silica. The Risdon works (Fig. 1) produces high-grade electrolytic zinc, leaded electrolytic zinc, zinc dust, cadmium, sulphuric acid and superphosphate. This paper, however, is concerned only with the zinc plant and process. Roasting The roasting of raw concentrate is not a major feature of Risdon's process, and in this respect practice is unlike that of most zinc plants. The roasting is mostly done on the Australian mainland at centers where the sulphuric acid made from the roaster gases can be used for superphosphate manufacture. A small amount, approximately 40 tons per day, is roasted at Risdon, acid being manufactured from the gases. The amount that can be roasted there is limited by the acid requirements of the zinc plant and of the superphosphate plant. Roasting is not carried to completion at the mainland plants, and the product, known as preroast calcine, largely constitutes the raw material for the Risdon zinc plant. It contains about 6 per cent of sulphur as sulphide. Roasting is completed at Risdon for reasons that are set out later in this paper. The zinc plant proper is divided into four main divisions: (1) final roasting division, (2) leaching and purification division, (3) electrolytic division, (4) melting and casting division. There are two subsidiary divisions—the cadmium division and the preroast, acid and superphosphate division.

Jan 1, 1937

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

From the cold Pacific waters in June rolls a blanket of white clouds that tucks up around the mountains at around 8000 or 9000 ft. This is the way it happens in southern Peru and so the mining operations and daily living at Toquepala have an ethereal quality not often encountered. Besides looking down on the clouds from the brightly sunlit mountain tops, one can discern the trace of a different era in the brown barren mountain slopes. This trace is like a delicate net laid over the surface of the earth-a criss-crossing of innumerable trails that are so omnipresent, yet faint, that the local people have long since ceased to notice them. It is difficult at first to ask about them because no one understands what you are talking about. It finally comes out though, that the markings are indeed trails, but fossil trails made by animals in times when they were in abundance in a countryside that was green in some bygone century. In a way Toquepala is still pristine, it is the way the engineers planned it-from the ground up. There are no additions or expansions- those tackings-on that spoil the symmetry of design while increasing the profit. This does not deny that annual production has gone up over the years. Daily mill throughput has been increased from 30,000 to 42,000 tpd. Initial design of the concentrator was for 30,000 tpd but in 1964-65 milling capacity was increased to 36,000 tpd at a cost of $3 million.

Jan 11, 1969

By Willard H. Mutchler, Henry S. Rawdon

As part of the study of the scratch-hardness method for metals and alloys in coöperation with one of the technical committees of the American Society for Testing Materials, the authors devoted considerable time to the study of the changes in hardness of metals when cold rolled. Various seemingly contradictory statements in the technical literature concerning the applicability of the serateh-hardness method to such cold-rolled materials were among the principal reasons for the investigation, the results of which are in part presented here. The effect of cold deformation, at least in moderate degrees, on the hardness as measured by the Brinell aid other common methods is so well known that further reference is unnecessary. Concerning the scratch hardness of cold-worked metals, Martens and Heyn state1 that hardness, whether measured by the ball-pressure rnethod (Kugeldruck) or by the scratch method (Ritzverfahren), will be increased by cold deformation. Jeffries and Archer give a seemingly diametrically opposite view. They state,2 that "the sclerometer (indicating scratch hardness) shows little difference between cold-worked and annealed metals." Portevin3 has shown that the rate at which the Brinell hardness of cold-worked copper and brass increases is very high for relatively slight deformation after which it drops to zero, while Merica and Walten-berg4 have observed that monel metal shows evidence of softening on

Jan 1, 1924